JP6589009B2 - Transfer material, recorded matter, and method for producing recorded matter - Google Patents

Description

The present invention relates to a transfer material on which an image is recorded, a recorded material on which an image recorded on the transfer material is transferred, and a method for manufacturing the recorded material .

  Patent Documents 1 and 2 propose a technique for transferring an image recorded by an ink jet method to a recorded material (a material to be transferred). For example, an image is recorded on the color material receiving layer of the transfer material by an inkjet method, and the transfer material and the recorded material are superposed and heated, whereby the color material receiving layer on which the image is recorded is transferred to the recorded material. The present inventors have also proposed a technique for controlling the molecular weight of the inorganic fine particles and the water-soluble resin in the color material receiving layer of the transfer material on which an image is formed by the inkjet method. (Patent Document 3).

JP 2006-517871 A JP-A-8-207450 JP2015-110321A

  In the ink jet system, in order to realize a sufficient image density, it is necessary to absorb a large amount of ink in the color material receiving layer of the transfer material, so that the color material receiving layer and the transfer material itself become thick. On the other hand, a recorded material such as a credit card is required to have a strong durability, for example, a durability that does not change even by a long-time immersion test with water. However, when the recorded material on which the color material receiving layer whose surface is covered with a transparent sheet (protective sheet) is transferred is immersed in water for a long time, the end of the color material receiving layer is exposed on the surface. The colorant receiving layer absorbs a large amount of moisture from its end. Therefore, in the subsequent drying process, there is a possibility that cracks and cracks may occur on the entire surface of the transparent sheet. Such a phenomenon is peculiar in an ink jet system that records an image by applying ink to the color material receiving layer, and does not occur in a thermal transfer system that does not require a color material receiving layer that absorbs water. That is, in the thermal transfer system, since the transfer layer is heated by a thermal head or the like to form an image, and then the transfer layer is transferred to the transfer material, a color material receiving layer that absorbs water is not required.

  Patent Documents 1, 2, and 3 do not describe the water resistance of the colorant receiving layer that absorbs such water. In patent document 3, in order to give a weather resistance to a transparent sheet (protective sheet), it is thickened to increase the strength. Therefore, although there is an effect of suppressing the occurrence of cracks and cracks that affect the water resistance of the colorant-receiving layer, it is difficult to achieve the high water resistance required for recorded matter such as credit cards.

An object of the present invention is to provide a transfer material, a recorded matter, and a method for producing the recorded matter that can achieve improvement in water resistance of the recorded matter .

The transfer material of the present invention is a transfer material in which a base sheet, a protective sheet, and a colorant receiving layer are laminated in this order, and the protective sheet has an average polymerization degree of 1,500 to 5,000. A transfer material comprising polyvinyl alcohol .

  According to the present invention, a recorded matter with excellent water resistance can be provided by releasing moisture in the colorant receiving layer to the outside through the protective sheet.

It is sectional drawing of a transfer material. It is explanatory drawing of the image recorded on a transfer material. It is explanatory drawing of the relationship between a swelling absorption type color material receiving layer and ink. It is explanatory drawing of the position alignment in a transcription | transfer process. It is sectional drawing for demonstrating the other example of a transfer material. It is explanatory drawing of the manufacturing stage of a recorded matter. It is sectional drawing for demonstrating the peeling process of a base material sheet. It is explanatory drawing of the image support body by which the transfer body was affixed on both surfaces. It is explanatory drawing of the 1st manufacturing apparatus of recorded matter. It is a block diagram for demonstrating the structure of the control system in the manufacturing apparatus of recorded matter. It is a block diagram for demonstrating the structure of the control system of the recording part in FIG. It is a flowchart for demonstrating operation | movement of a manufacturing apparatus. It is explanatory drawing of the 2nd manufacturing apparatus of recorded matter. It is explanatory drawing of the printer which records an image on a transfer material. It is explanatory drawing of the relationship between the printer of FIG. 16, and a transfer material. It is explanatory drawing of the transfer part which heat-presses a transfer material to an image support body. It is explanatory drawing of the relationship between the printer part in the 6th manufacturing apparatus of recorded matter, and a transfer material. It is explanatory drawing of the printer part in the 7th manufacturing apparatus of recorded matter. It is explanatory drawing of the transfer part in the 7th manufacturing apparatus of recorded matter. It is explanatory drawing of the 8th manufacturing apparatus of recorded matter. It is explanatory drawing of the printer part in the 9th manufacturing apparatus of recorded matter. It is sectional drawing of the transfer material of a different structural example. It is explanatory drawing of the manufacturing method of recorded matter. It is explanatory drawing of the other example of the manufacturing method of recorded matter. It is explanatory drawing of the further another example of the manufacturing method of recorded matter. It is explanatory drawing of the further another example of the manufacturing method of recorded matter. It is explanatory drawing of the recording device containing a punching process part. It is explanatory drawing of the 2nd manufacturing apparatus of recorded matter. It is explanatory drawing of the 3rd manufacturing apparatus of recorded matter. It is explanatory drawing of the 4th manufacturing apparatus of recorded matter. It is explanatory drawing of the 5th manufacturing apparatus of recorded matter. It is explanatory drawing of the generation | occurrence | production mechanism of the crack in the immersion water resistance test of a transparent sheet. It is sectional drawing of the recorded matter of a different structural example. It is sectional drawing of the recorded matter after an immersion water resistance test. It is sectional drawing for demonstrating the state which contaminated water adhered to the surface of the transparent sheet. It is explanatory drawing of the example from which the formation method of the pore by foaming differs. It is explanatory drawing of the example from which the formation method of the pore by a porous particle differs. It is explanatory drawing of the example from which the formation method of the pore by a hollow particle differs. It is explanatory drawing of the example from which the punching process with respect to a transparent sheet differs. It is explanatory drawing of the other different example of the punching process with respect to a transparent sheet. It is explanatory drawing of the further another example of the punching process with respect to a transparent sheet. It is explanatory drawing of the further another example of the punching process with respect to a transparent sheet. It is explanatory drawing of an extending | stretching processing apparatus. It is explanatory drawing of a craze processing apparatus. It is explanatory drawing of the example from which the formation method of the pore by a crazing process differs. It is explanatory drawing of the example from which a punching processing method differs. It is explanatory drawing of the further another example of the manufacturing method of recorded matter. It is explanatory drawing of the further another example of the manufacturing method of recorded matter. It is explanatory drawing of the further another example of the manufacturing method of recorded matter. It is explanatory drawing of the example from which the formation method of the pore in the 6th manufacturing apparatus of recorded matter differs. It is explanatory drawing of the example from which the transcription | transfer part differs in the 6th manufacturing apparatus of recorded matter. It is explanatory drawing of the example from which the formation method of the pore in the 7th manufacturing apparatus of recorded matter differs. It is explanatory drawing of the example from which the transcription | transfer part differs in the 7th manufacturing apparatus of recorded matter. It is explanatory drawing of the example from which the formation method of the pore in the 8th manufacturing apparatus of recorded matter differs. It is explanatory drawing of the example from which the formation method of the pore in the 9th manufacturing apparatus of recorded matter differs. It is explanatory drawing of the example from which the formation method of the pore in the 6th manufacturing apparatus of recorded matter differs. It is explanatory drawing of the structural example of the independent punching part. It is explanatory drawing of the other structural example of the independent punching process part. It is sectional drawing after the recorded material in 2nd invention was immersed in water for a long time. It is a cross section of the recorded matter in 2nd invention. It is explanatory drawing of the example from which the recorded matter containing a multi-layered transparent sheet differs. It is explanatory drawing of the example from which the transfer material containing a multilayered transparent sheet differs. It is explanatory drawing of the state which contaminated water adhered to the recorded matter. It is explanatory drawing of the other example of the state which contaminated water adhered to the recorded matter. It is explanatory drawing of the structural example of a recording device. It is sectional drawing for demonstrating the example from which the transfer material provided with the primer layer differs. It is a perspective view for demonstrating the process of peeling a base material sheet. It is sectional drawing of the transfer material in 2nd invention. It is sectional drawing of the recorded matter in 2nd invention. It is explanatory drawing of the example from which the manufacturing method of the recorded matter in 2nd invention differs. It is explanatory drawing which shows the state which heat-pressed the transfer material of this invention to the image support body.

  Hereinafter, the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and includes all objects having the invention-specific matters. In addition, about the member of the same structure, the same code | symbol is attached | subjected in drawing, The description may be abbreviate | omitted.

  As a result of intensive studies on the above-described problems, the present inventors have found an inkjet recorded product that can prevent cracking of a transparent sheet (protective sheet) that occurs when the inkjet recorded product is immersed in water for a long time. Could be realized. First, the mechanism of cracking of a transparent sheet after immersion water resistance in a conventional inkjet recording material will be described with reference to the drawings.

  FIG. 32 is a cross-sectional view showing a conventional general inkjet recorded matter before the immersion water resistance test. This ink jet recording has a structure in which a transparent sheet 52, a color material receiving layer 53, and an image support 55 are sequentially laminated. Since the surface of the color material receiving layer 53 is covered with the transparent sheet 52 made of a water-insoluble resin, it cannot absorb moisture. However, since the end portion 517 of the color material receiving layer 53 is exposed to the outside, a large amount of moisture is absorbed from the end portion 517 when the ink-jet recorded material is immersed in water.

  FIG. 32 shows a change when the ink jet recorded material is immersed in water for a long time and then taken out from water. The colorant receiving layer 53 expands greatly when absorbing a large amount of water from its end 517. Portion 519 is an expanded portion. Note that the color material receiving layer 53 alone may expand about 1.5 times when immersed for 48 hours. Next, when the ink-jet recorded matter is taken out of water, evaporation of moisture in the color material receiving layer 53 starts. At this time, since the surface of the colorant receiving layer 53 is covered with the transparent sheet 52, the water does not evaporate from the surface, but the water evaporates only from the end portion 517 exposed to the outside. Therefore, in the color material receiving layer 53 in which the water has evaporated, the portion 519 that has expanded during water absorption contracts like the portion 520. Since the color material receiving layer 53 starts to contract from the end portion 517 thereof, stress at the time of contraction is concentrated on the central portion 518 of the transparent sheet 52 as indicated by an arrow E in the drawing. Therefore, a crack is generated in the portion 518 of the transparent sheet 52, and in some cases, a portion of the portion 518 may be broken and a crack may be generated on the surface.

  In other words, the colorant receiving layer that has once absorbed and expanded over the entire surface is dried and shrunk sequentially from its end portion, loses its flexibility, and is fixed to the image support. As a result, while the strain gradually accumulates on the center side of the color material receiving layer that is still swollen with water, the drying shrinkage gradually proceeds to the center of the color material receiving layer. In this way, the accumulated strain concentrates on the colorant receiving layer and the transparent sheet portion that dry and shrinks with delay, and cracks and cracks occur on the transparent sheet portion that cannot withstand the stress during shrinkage. It is thought to occur.

  As described above, the cause of cracks in the transparent sheet is that the evaporation of moisture from the colorant receiving layer is performed only from the end, and the stress of the contraction is concentrated in one specific place or a plurality of specific places on the transparent sheet. There is. The present invention pays attention to such points, and has established a configuration that disperses the stress of the transparent sheet caused by the absorption and evaporation of moisture into the colorant receiving layer. In other words, in the present invention, the transparent sheet serving as the surface of the recorded material (transfer material) is provided with a passage through which moisture is discharged, thereby removing unnecessary moisture absorbed by the color material receiving layer over the entire surface of the transparent sheet. Evaporate for a while. In this way, cracks in the transparent sheet in the immersion water resistance test could be eliminated by dispersing the stress concentration on the transparent sheet in the course of drying of the colorant receiving layer that has absorbed water for a while.

(First invention)
The first invention will be described below.

  The transparent sheet functions as a protective sheet that protects the surface of the recorded matter. In the first invention, the transparent sheet that is the surface of the recorded matter is provided with pores that penetrate to the colorant receiving layer. ing. 33 (a) to 33 (f) show a recorded material created by transferring the color material receiving layer 53 and the transparent sheet 52 of the transfer material of the present invention to a support 55 of the recorded material. A reverse image 72 is recorded on the color material receiving layer 53 as described later. Since the transparent sheet 52 in the present invention has the pores 52A, the water absorbed in the colorant receiving layer 53 is evaporated from the surfaces 521, 553, 554, and 555 of the transparent sheet 52 through the pores 52A of the transparent sheet 52. Can do. The recorded material only needs to have pores 52A formed at least in the transparent sheet 52 as shown in FIG. 33 (a), and the pores 53A also exist in the colorant receiving layer 53 as shown in FIGS. 33 (b) and 33 (c). May be formed. Also, as shown in FIGS. 33 (d) to (f), a large number of voids are formed in the transparent sheet 52, and the open cell structures 553, 554 are continuous so as to form pores 52A penetrating the transparent sheet 52. It may be 555. These pores will be described later. The pores 52A of the transparent sheet 52 are configured such that the transparent sheet 52 can exhibit moisture permeability or moisture permeability. That is, the pores 52A have the property that the water in contact with the transparent sheet 52 passes through the transparent sheet 52 in a liquid state or a gas state.

  FIG. 34A shows a state in which the recorded matter of FIG. 33 is immersed in water for a long time and then taken out from water. When the recorded matter 73 of the present invention is taken out of water, the moisture absorbed in the color material receiving layer 53 evaporates not only from the end portion 517 of the color material receiving layer 53 but also from the surface 521 of the transparent sheet 52. In this way, by evaporating the moisture of the color material receiving layer from the surface of the transparent sheet, the stress at the time of contraction of the color material receiving layer is widely dispersed over the entire surface of the transparent sheet as indicated by arrow C. As a result, Can prevent cracking of transparent sheet.

  As shown in FIGS. 23 to 26 and FIGS. 47, 48, and 49, the recorded material in the present embodiment first has a reverse image 72 formed on a color material receiving layer 53 of a transfer material by an ink jet recording head 607. Record (step 1). Next, the transfer material and the image support 55 are heat-pressed using the heat roller 21 to transfer the transfer material to the image support 55 (step 2). Finally, the base material sheet 50 of the transfer material is peeled using the peeling roll 88 (Step 3) to obtain a recorded matter in which the color material receiving layer on which the image is recorded and the protective sheet are laminated. The transparent sheet 52 serving as the surface of the recorded material has pores 52A.

[1] Transfer Material The transfer material of the present embodiment is a transfer material for ink jet recording having a laminated structure in which a base sheet, a transparent sheet, and a color material receiving layer are laminated in this order as described above. The transparent sheet can release moisture out of the system. More preferably, the transfer material is characterized in that the color material receiving layer contains at least a water-soluble resin, and the transparent sheet has at least moisture permeability or moisture permeability due to its pore structure. More preferably, the transparent sheet is characterized by being moisture permeable and moisture permeable. 22A to 22H are cross-sectional views of different configuration examples of the transfer material. The transfer material 1 has a laminated structure in which a base sheet 50, a transparent sheet 52, and a color material receiving layer 53 are laminated in this order. The colorant receiving layer 53 in FIGS. 22A to 22E contains at least a water-soluble resin capable of absorbing moisture, and at least the transparent sheet 52 has pores 52A formed therein. The material sheet 50 and the color material receiving layer 53 are communicated with each other.

  The transfer material 1 in FIG. 22A has pores 52A formed only in the transparent sheet 52, and the transfer material 1 in FIG. 22B has pores 52A formed in the transparent sheet 52 and a color material receiving layer. 53 also has pores 53A. In the transfer material 1 in FIG. 22C, pores 52 </ b> A are formed in the transparent sheet 52, and pores 50 </ b> A are also formed in the base material sheet 50. In the transfer material 1 of FIGS. 22D and 22E, pores 52A, 53A, and 50A are formed in the transparent sheet 52, the color material receiving layer 53, and the base material sheet 50, respectively. Further, in the transparent sheet 52 of FIGS. 22 (f) to 22 (h), a large number of voids are formed in the transparent sheet 52 so as to penetrate between both surfaces. These voids form continuous bubble structures 553, 554, and 555 that are continuous so as to form pores 52A that penetrate the transparent sheet 52.

  In such a transfer material 1, after an image is recorded on the color material receiving layer 53, the color material receiving layer 53 is transferred together with the transparent sheet 52 to the image support 55 of the recorded material as shown in FIG. Therefore, the transfer material 1 functions as an intermediate sheet including the color material receiving layer 53 and the transparent sheet 52 transferred to the recorded matter. FIG. 33 (a) is a recorded material created using the transfer material 1 of FIG. 22 (c), and FIG. 33 (b) is created using the transfer material 1 of FIG. 22 (c) or (d). FIG. FIG. 33 (c) is a cross-sectional view of a recorded matter created using the transfer material 1 of FIG. 22 (b) or (e). FIGS. 33D, 33E, and 33F are cross-sectional views of recorded matter created using the transfer material 1 shown in FIGS. 22F, 22G, and 22H, respectively. As the transfer material 1, as shown in FIG. 1B, the transparent sheet 52 in which the pores 52A are not formed in advance can be used. In this case, the pores 52 </ b> A may be formed in the transparent sheet 52 before and after any of the steps 1 to 3.

[1-1] Color Material Receiving Layer The color material receiving layer is a layer that receives ink by an ink jet recording method and contains at least a water-soluble resin. The colorant receiving layer is mainly composed of a water-soluble resin, contains a swelling absorption type that accepts ink in a network structure of a water-soluble polymer, contains a water-soluble resin and at least inorganic fine particles, and has a fine void structure. Either a void absorbing type for receiving ink or a colorant receiving layer can be used.

  When the color material receiving layer 53 is a swelling absorption type color material receiving layer mainly composed of a water-soluble resin, the absorption speed of water is slow, so even when the recorded matter is immersed in water, the color material receiving layer 53 can be obtained in a short period of time. If it exists, the crack of a transparent sheet (52) does not arise easily. Although the recorded matter to which the color material receiving layer 53 is transferred is somewhat advantageous from the viewpoint of water resistance, the ink absorption speed in the color material receiving layer 53 is also slow. Therefore, although the swelling absorption type colorant receiving layer functions sufficiently under the limited conditions, the recording speed of the image is limited and may not be suitable for high-speed recording. In the case of a swelling absorption type color material receiving layer, the color material receiving layer swells due to moisture in the ink, and irregularities are generated on the surface of the color material receiving layer. There is a risk of reducing the adhesion.

  On the other hand, the void-type color material receiving layer is composed of a composition containing a water-soluble resin and at least inorganic fine particles. In the case where the color material receiving layer 53 is of the gap absorption type, when the recorded material is immersed in water, as described above, water can more easily enter from the color material receiving layer at the end of the recorded material, thereby improving water resistance. Problems arise and cracks and cracks of the transparent sheet are likely to occur. However, in the present invention, by providing pores in the transparent sheet, even if the color material transfer layer absorbs a large amount of moisture, the transparent sheet is not easily cracked or cracked due to stress concentration. . Further, since the void formed by the inorganic fine particles can absorb the ink quickly, the gap absorption type color material receiving layer can perform high-speed inkjet recording. Further, unlike the swelling type color material receiving layer, the space absorption type color material receiving layer is kept smooth without swelling. In particular, when a pigment ink is used, the pigment component in the pigment ink is fixed on the surface of the color material receiving layer, while the moisture and solvent components in the ink penetrate into the color material receiving layer and the pigment component. (Solid-liquid separation). Therefore, the surface of the colorant receiving layer is in a dry state at the time of transfer. Since the surface of the colorant receiving layer is in a dry state due to the voids formed by the inorganic fine particles, the moisture or solvent in the ink suddenly boils when the transfer material is heat-pressed to the image support of the recorded material. It is suppressed. As a result, it is possible to suppress the poor adhesion that the transfer material and the support for the recorded material are not sufficiently in contact, and the generation of remaining bubbles that remain between the transfer material and the image support for the recorded material.

  In addition, since the color material receiving layer contains inorganic fine particles, when the transfer material base sheet is peeled off after transfer, cracks are easily formed in the gaps between the inorganic fine particles of the color material receiving layer, and the edges of the recorded material are reduced. It is possible to prevent burrs from remaining in the part. Therefore, the color material receiving layer 53 is preferably a void absorption type color material receiving layer. That is, according to the present invention, high-speed recording of an image using a gap absorption type color material transfer layer is possible without impairing water resistance.

[1-1-1] Inorganic fine particles The inorganic fine particles are fine particles made of an inorganic material. The inorganic fine particles have a function of forming voids for receiving the color material in the color material receiving layer.

  There is no restriction | limiting in particular as a kind of inorganic material which comprises an inorganic fine particle. However, it is preferably an inorganic material that has high ink absorbability, excellent color developability, and can form a high-quality image. For example, calcium carbonate, magnesium carbonate, kaolin, clay, talc, hydrotalcite, aluminum silicate, calcium silicate, magnesium silicate, diatomaceous earth, alumina, colloidal alumina, aluminum hydroxide, boehmite structure alumina hydrate, pseudo boehmite structure And alumina hydrate, lithopone (a mixture of barium sulfate and zinc sulfide), zeolite and the like.

  Among the inorganic fine particles made of these inorganic materials, alumina fine particles made of at least one substance selected from the group consisting of alumina and alumina hydrate are preferable. Examples of the alumina hydrate include boehmite-structured alumina hydrate and pseudoboehmite-structured alumina hydrate. Alumina, boehmite-structured alumina hydrate, and pseudoboehmite-structured alumina hydrate are preferred in that the transparency of the colorant-receiving layer and the image recording density can be improved.

  Boehmite-structured alumina hydrate can be obtained by adding an acid to a long-chain aluminum alkoxide for hydrolysis and peptization (see JP-A-56-120508). Either an organic acid or an inorganic acid may be used for peptization. However, it is preferable to use nitric acid. By using nitric acid, the reaction efficiency of hydrolysis can be improved, an alumina hydrate having a controlled shape can be obtained, and a dispersion having good dispersibility can be obtained.

  The inorganic fine particles preferably have a precisely controlled average particle size, and the average particle size is preferably 120 to 200 nm. By setting the average particle size to preferably 120 nm or more, and more preferably 140 nm or more, it is possible to improve the ink absorbability of the colorant receiving layer and to suppress ink bleeding and beading in the image after recording. . On the other hand, when the average particle diameter is preferably 200 nm or less, more preferably 170 nm or less, light scattering by the inorganic fine particles can be suppressed and the transparency of the colorant receiving layer can be improved. Further, since the number of inorganic fine particles per unit area of the colorant receiving layer can be increased, ink absorbability can be improved. Accordingly, the recording density of the image can be improved, and dullness of the image after recording can be suppressed. Thereby, the transparency (transmittance) of the color material receiving layer and the visibility of the image from the transparent sheet side can be improved. Even when a pigment ink that does not easily penetrate into the color material receiving layer is used as the color material, it is not necessary to increase the thickness of the color material receiving layer in order to increase the ink application density and accept a large amount of ink. . For this reason, it is possible to reduce the thickness of the transfer material and the entire recorded material.

  As the inorganic fine particles, known inorganic fine particles may be used as they are, or those obtained by adjusting the average particle diameter and polydispersity index of known inorganic fine particles using a pulverizer / disperser may be used. There are no particular restrictions on the type of pulverizer. For example, a conventionally known pulverizer such as a high-pressure homogenizer, an ultrasonic homogenizer, a wet media type pulverizer (sand mill, ball mill), a continuous high-speed agitation type disperser, or an ultrasonic disperser can be used.

  More specific examples of the pulverizing and dispersing machine are as follows: Manton Gorin homogenizer, Sonator (above, manufactured by Doei Sei); Microfluidizer (manufactured by Mizuho Industries); Nanomizer (manufactured by Tsukishima Kikai); Pearl mill, Glen mill, Tornado (above Asada Steel); Visco mill (Imex); Mighty mill, RS mill, SΓ mill (Inoue Seisakusho); Sugawara Milder (Ebara Seisakusho); Fine Flow Mill, Cavitron (made by Taiheiyo Kiko);

The inorganic fine particles preferably satisfy the range of the average particle diameter and have a polydispersity index (μ / <Γ> ² ) of 0.01 to 0.20, preferably 0.01 to 0.18. More preferably. By setting the particle size within the above range, the particle size can be kept constant, so that the glossiness and transparency of the colorant-receiving layer can be improved. Accordingly, the recording density of the image can be improved, and dullness of the image after recording can be suppressed.

The average particle diameter and polydispersity index referred to in this specification are the values measured by the dynamic light scattering method, “polymer structure (2) scattering experiment and morphology observation Chapter 1 light scattering” (Kyoritsu Publishing High Edited by Molecular Society), or J. Org. Chem. Phys. , 70 (B), 15 ApI. 3965 (1979). According to the theory of dynamic light scattering, when fine particles having different particle diameters are mixed, there is a distribution in the decay of the time correlation function from the scattered light. By analyzing this time correlation function by the cumulant method, the average (<Γ>) and dispersion (μ) of the decay rate can be obtained. Since the decay rate (Γ) is expressed as a function of the particle diffusion coefficient and the scattering vector, the hydrodynamic average particle diameter can be obtained using the Stokes-Einstein equation. Therefore, the polydispersity index (μ / <Γ> ² ) obtained by dividing the dispersion of the decay rate (μ) by the mean square (<Γ> ² ) represents the degree of dispersion of the particle size, and the value is zero. The closer it is, the narrower the particle size distribution. The average particle size and polydispersity index defined in the present embodiment can be easily measured using, for example, a laser particle size analyzer PARIII (manufactured by Otsuka Electronics).

  An inorganic fine particle can be used individually by 1 type or in mixture of 2 or more types. “Two or more types” includes not only materials different from each other but also materials having different characteristics such as average particle diameter and polydispersity index.

[1-1-2] Water-soluble resin The water-soluble resin is a resin that is sufficiently mixed with water at 25 ° C. or has a solubility in water of 1 (g / 100 g) or more. In the case of the swelling type colorant receiving layer, the water-soluble resin acts as a layer for receiving ink in the network structure of the water-soluble polymer. In the case of the void absorption type, the water-soluble resin functions as a binder for binding the inorganic fine particles.

The water-soluble resin is not particularly limited as long as it satisfies the following formula (1). When | ΔSP | is 0.6 or more, the intermolecular force between the water-soluble resin and the emulsion E1 described later is weakened, the adhesion between the colorant-receiving layer and the transparent sheet is lowered, and in the test such as tape peeling, Since peeling occurs between the colorant receiving layer and the colorant receiving layer, it is not preferable. By setting | ΔSP | in the range of the following formula (1), the water-soluble resin and the emulsion E1 can be strongly bonded by the intermolecular force, and the adhesion between the transparent sheet and the colorant receiving layer can be improved.
0 ≦ ΔSP ≦ 0.6 (1)

For example, starch, gelatin, casein and modified products thereof;
Cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose;
Polyvinyl alcohol (complete saponification, partial saponification, low saponification, etc.) or a modified product thereof (cation modified product, anion modified product, silanol modified product, etc.);
Urea resin, melamine resin, epoxy resin, epichlorohydrin resin, polyurethane resin, polyethyleneimine resin, polyamide resin, polyvinyl pyrrolidone resin, polyvinyl butyral resin, poly (meth) acrylic acid or copolymer thereof And resins such as resins, acrylamide resins, maleic anhydride copolymer resins, and polyester resins.

  Among water-soluble resins, polyvinyl alcohol, particularly saponified polyvinyl alcohol obtained by hydrolyzing (saponifying) polyvinyl acetate is preferable. The SP value of polyvinyl alcohol is close to the SP value of PVC and PET-G described later. Therefore, when the water-soluble resin and the image support are melted by heat at the time of transfer, the compatibility of both increases, and the water-soluble resin is firmly bonded to the image support. Polyvinyl alcohol can improve the adhesion (transfer performance) between the image support and the colorant receiving layer when PVC or PET-G is used as the image support, and is particularly preferably used.

  The colorant receiving layer is preferably made of a composition containing polyvinyl alcohol having a saponification degree of 70 to 100 mol%. The degree of saponification means the percentage of the number of moles of hydroxyl groups relative to the total number of moles of acetate groups and hydroxyl groups of polyvinyl alcohol.

  By setting the saponification degree to 70 mol% or more, more preferably 86 mol% or more, an appropriate hardness can be imparted to the colorant receiving layer. Therefore, the foil breakability of the colorant receiving layer is improved in the peeling step, and the occurrence of burrs at the end can be suppressed. Moreover, the viscosity of the coating liquid containing inorganic fine particles and polyvinyl alcohol can be reduced. Therefore, it becomes easy to apply the coating liquid to the transparent sheet, and the productivity of the transfer material can be improved. On the other hand, when the degree of saponification is preferably 100 mol% or less, more preferably 90 mol% or less, moderate flexibility can be imparted to the color material receiving layer. Thereby, the adhesive strength between the transparent sheet and the color material receiving layer can be improved, and the peeling of the color material receiving layer from the transparent sheet due to insufficient adhesive strength can be suppressed. Moreover, moderate hydrophilicity can be imparted to the colorant receiving layer, and the ink absorbability is improved. Therefore, a high-quality image can be recorded on the color material receiving layer.

  As saponified polyvinyl alcohol satisfying the range of saponification degree, fully saponified polyvinyl alcohol (saponification degree 98-99 mol%), partially saponified polyvinyl alcohol (saponification degree 87-89 mol%), low saponified polyvinyl alcohol (saponification degree 78-82 mol%). And the like. Among these, partially saponified polyvinyl alcohol is preferable.

  The colorant receiving layer is preferably made of a composition containing polyvinyl alcohol having an average degree of polymerization of 2,000 to 5,000.

  When the average degree of polymerization is preferably 2,000 or more, more preferably 3,000 or more, moderate flexibility can be imparted. Therefore, the foil breakability of the colorant receiving layer is improved in the peeling step, and the occurrence of burrs at the end can be suppressed. On the other hand, when the average degree of polymerization is preferably 5,000 or less, more preferably 4,500 or less, an appropriate hardness can be imparted to the colorant receiving layer. Thereby, the adhesive strength between the transparent sheet and the color material receiving layer can be improved, and the peeling of the color material receiving layer from the transparent sheet due to insufficient adhesive strength can be suppressed. Moreover, the viscosity of the coating liquid containing inorganic fine particles and polyvinyl alcohol can be reduced. Therefore, it becomes easy to apply the coating liquid to the transparent sheet, and the productivity of the transfer material can be improved. In addition, the pores of the colorant receiving layer can be prevented from being filled, the opening state of the pores can be kept good, and the ink absorbability is good. Therefore, a high-quality image can be recorded on the color material receiving layer.

  The average degree of polymerization is a value calculated according to the method described in JIS-K-6726.

  A water-soluble resin can be used individually by 1 type or in mixture of 2 or more types. “Two or more” includes those having different characteristics such as saponification degree and average degree of polymerization.

  The amount of the water-soluble resin is preferably 3.3 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine particles. When the amount of the water-soluble resin is preferably 3.3 parts by mass or more, more preferably 5 parts by mass or more, the colorant receiving layer is less likely to crack or fall off. On the other hand, when the amount of the water-soluble resin is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, the ink absorbability is improved.

[1-1-3] Cationic resin The cationic resin is a resin having a cationic atomic group (for example, quaternary ammonium or the like) in the molecule. Further, the SP value of the cationic resin not only shows a value close to the SP value of the resin constituting the image support, but is easily melted by heat when the transfer material is thermocompression bonded to the image support. Since electrostatic bonding is also promoted, the adhesion between the image support and the colorant receiving layer can be further strengthened, and the adhesion (transfer performance) between the image support and the colorant receiving layer can be improved. . That is, since the cationic resin generally binds electrostatically with negatively charged ink, the ink can be fixed in the colorant receiving layer. In addition to this function, the cationic resin is ( 1) Since a value close to the SP value of the image support is selected, the affinity to the image support is high, and the adhesion between the image support and the colorant receiving layer during transfer is improved. be able to. In addition, the cationic resin (2) has a low melting point and is easily melted by heat at the time of transfer, thereby further strengthening the adhesion between the image support and the colorant receiving layer. Furthermore, since the cationic resin used in the present invention has a small molecular weight, (3) even if the addition amount to the color material receiving layer is small, many molecules can be added to the color material receiving layer. Therefore, a cationic group that can be electrostatically bonded to a negatively charged image support in general can be interposed on the surface of the colorant receiving layer, and as a result, the adhesion to the image support can be improved. Can do. Furthermore, (4) Adhesiveness with a resin-dispersed pigment described later can be enhanced. That is, since the SP value of the dispersed resin of the resin dispersed pigment is close to the SP value of the cationic resin, when the cationic resin and the dispersed resin are melted by the heat during transfer, the compatibility between the two increases. It is firmly bonded to the receiving layer. Thereby, the transfer performance of the color material receiving layer to the image support is improved. Furthermore, (5) the emulsion used as the main component of the transparent sheet is negatively charged, and can firmly adhere to the cationic resin, thereby enhancing the adhesion between the transparent sheet and the colorant receiving layer. Therefore, the cationic resin used in the present invention plays the role of enhancing the transfer performance of the color material receiving layer to the image support due to the above five effects.

  As such a cationic resin, it is preferable to use at least one polymer selected from, for example, polyallylamine (for example, allylamine polymer, diallylamine polymer, etc.) and urethane polymer. Among these, the low-molecular polyallylamine described below particularly has (1) a melting point as low as about 80 ° C., and is easily melted when a transfer material is heat-pressed on an image support, and (2) a molecular structure is small. Therefore, a large amount of cationic groups per unit area can be present on the surface of the colorant receiving layer, and electrostatic bonding to the image support can be promoted.

  The polyallylamine is preferably at least one polyallylamine represented by the following general formula (8).

(Wherein R ³ , R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkanol group, an allylalkyl group or an allylalkenyl group. Also, R ³ , R ⁴ and R ⁵ may be the same or different from each other, X ⁻ represents an inorganic or organic anion, and n is an integer indicating the degree of polymerization.

  The weight average molecular weight of the cationic resin is preferably 1,000 to 15,000, more preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000. By making the weight average molecular weight within the range, the stability of the coating liquid can be improved, and the voids of the colorant receiving layer are hardly reduced, and the colorant absorbability can be maintained. Further, when the molecular weight of the cationic resin is 5,000 or less, more cationic groups (that is, adsorption sites that perform electrostatic bonding) are more distributed on the surface of the colorant receiving layer in contact with the image support to support the image. The adhesion (transfer performance) between the body and the colorant receiving layer can be further improved. When the average molecular weight is larger than 15000, the surface of the color material receiving layer in contact with the image support has fewer cationic groups (that is, adsorption sites that perform electrostatic bonding), and thus the adhesion to the color material receiving layer ( Transfer performance) decreases. On the other hand, when the weight average molecular weight is less than 1000, the cationic resin moves inside the color material receiving layer together with the ink solvent at the time of printing, and the amount of cationic groups distributed on the surface of the color material receiving layer is reduced. Absent

  The amount of the cationic resin used is preferably 0.01 to 5% by mass and more preferably 0.01 to 3% by mass with respect to the inorganic fine particles (alumina hydrate or the like). When the amount of the cationic resin used exceeds the above range, the dispersion of the inorganic fine particles and the viscosity of the coating liquid obtained by adding a binder to the dispersion liquid become high, and the storage stability and coating property of the dispersion liquid or the coating liquid are increased. May decrease.

  The melting point of the cationic resin is preferably 60 to 160 ° C. By setting the melting point of the cationic resin within the above-mentioned range, the cationic resin can be melted when the transfer material is thermocompression-bonded to the image support, and the adhesion between the image support and the colorant receiving layer can be achieved. (Transfer performance) can be improved.

[1-1-4] Thickness The thickness of the colorant receiving layer is not particularly limited, but it is preferably thick from the viewpoint of ink absorbability. On the other hand, in the recorded matter of the present invention, since the image information is viewed from the transparent sheet side opposite to the ink jet recording surface, it is necessary to consider the transparency of the colorant receiving layer itself. Although depending on the droplet diameter of inkjet recording, the thickness of the colorant receiving layer may be 40 μm or less from the viewpoint of the balance between ink absorbability and thermocompression transferability and expansion / contraction properties during moisture absorption. preferable. More preferably, by setting the thickness to 30 μm or less, the transparency of the colorant-receiving layer can be further improved, and the heat conduction is further improved when transferring the image to the image support by thermocompression bonding. The adhesion (transfer performance) with the material receiving layer can be further improved. Furthermore, it is possible to reduce the stress due to expansion and contraction of the colorant receiving layer during water absorption.

  On the other hand, depending on the ink droplet diameter in inkjet recording, good image recording may be possible if the thickness of the colorant receiving layer is 2 μm or more. More preferably, when the thickness of the colorant receiving layer is 5 μm or more, the ink absorbability can be stably secured, and the ink absorption speed and the ink fixability are improved. That is, the thickness of the color material receiving layer is more preferably 5 to 30 μm. In the present invention, in addition to the balance of the thickness of the transparent sheet and the colorant receiving layer, the structure of the pores needs to be appropriately selected according to the application. Further, when a plastic card is used as the image support, it is necessary to suppress the thickness of the entire recorded matter to a total thickness of 0.84 mm or less described in JIS6301. In this case, it is preferable from the viewpoint of practical balance design that the colorant receiving layer has a minimum thickness that enables good ink jet recording.

[1-2] Transparent Sheet The transfer material 1 includes a transparent sheet 52 as shown in FIG. 22, and the transparent sheet 52 includes a passage that can release moisture in the color material receiving layer to the outside. . Specifically, the transparent sheet 52 has pores 52 </ b> A penetrating between the base material sheet 50 and the color material receiving layer 53 as described above. Further, when using the transfer material 1 in which the pores 52A are not formed in advance in the transparent sheet 52 as shown in FIG. 1B, at least before the transfer material 1 before and after any of the steps 1 to 3. The pore 52A is formed in the transparent sheet 52.

  The pores are configured so that the transparent sheet can exhibit moisture permeability or moisture permeability. That is, the transparent sheet has a property of allowing water in contact therewith to pass through in a liquid state or a gas state. Therefore, in the recorded matter of the present invention, as shown in FIG. 34 (b), even in a water resistance test in which a large amount of moisture is absorbed by the color material receiving device 53 and dried, moisture is absorbed from the entire surface of the transparent sheet 52. Evaporation is released and cracking is suppressed.

  Thus, the transparent sheet is permeable to moisture, and effectively suppresses the occurrence of cracks due to water absorption and evaporation of the colorant receiving layer. After creation of the recorded material, the moisture-permeable transparent sheet having pores that penetrate to the colorant receiving layer can pass water vapor 550 as shown in FIG. Can pass through. Therefore, the evaporation of the water absorbed by the color material receiving layer from the entire surface of the transparent sheet is promoted.

[1-2-1] Size of pores When a recorded material is immersed in water, air present inside the pores of the transparent sheet forms a meniscus of water at the entrance of the pores. Absorption of water from the surface of the transparent sheet can be suppressed. For this purpose, the pore size is preferably 100 μm or less. Further, when a large amount of water is absorbed in the color material receiving layer, a meniscus of water is hardly formed at the entrance of the pores in contact with the color material receiving layer. Therefore, by reducing the diameter of the pores, it can act as a capillary tube, transporting moisture in the colorant receiving layer to the surface of the transparent sheet through the pores of the transparent sheet, thereby promoting its evaporation. it can.

  When the thickness of the transparent sheet is sufficiently large relative to the thickness of the colorant receiving layer, a certain amount of moisture can be transmitted by setting the pore size of the transparent sheet in the range of 100 to 300 μm. It can prevent the occurrence of cracks. That is, since the transparent sheet has sufficient strength if it is sufficiently thick relative to the thickness of the colorant receiving layer and can absorb the stress of water absorption expansion and drying shrinkage, the transparent sheet has water permeability and moisture permeability. Even if it is low, cracks are unlikely to occur. However, when the thickness of the transparent sheet is remarkably thin relative to the thickness of the color material receiving layer, the strength of the transparent sheet is relatively low, and the shrinkage of the color material receiving layer is relatively large. Cracks tend to occur. In this case, the water permeability and moisture permeability of the transparent sheet must be increased. For example, by arranging fine pores of 100 μm or less at a high density, water permeability and moisture permeability per unit area can be improved and cracking can be prevented. On the other hand, when the pore size exceeds 300 μm, the effect of preventing cracking can be expected to be further increased. However, when the recorded material is immersed in water, the meniscus of water at the entrance of the pore It becomes difficult to form. In this case, water absorption of the color material transfer layer through the transparent sheet is promoted, but liquid stains and the like easily enter. Therefore, the size of the pores needs to be selected in a preferable range depending on the application.

[1-2-2] Thickness The thickness of the transparent sheet is not particularly limited. In addition to the effect of the pores of the transparent sheet, the water resistance can be further improved by setting the thickness of the transparent sheet in relation to the thickness of the colorant receiving layer. That is, as described above, since the transparent sheet has sufficient strength if the thickness thereof is sufficiently larger than the thickness of the colorant receiving layer, even if the water permeability and moisture permeability are small, cracks are unlikely to occur. However, when the thickness of the transparent sheet is smaller than the thickness of the colorant receiving layer, the strength of the transparent sheet becomes relatively small and cracking is likely to occur, so that the moisture permeability and water permeability of the transparent sheet are increased. There must be. As described above, the water permeability and moisture permeability of the transparent sheet can be controlled by the average diameter of the pores and the density of the pores. The ratio (A / B) between the thickness (A) of the transparent sheet and the thickness (B) of the colorant receiving layer is preferably in the range of the following formula (1A).
0.07 ≦ A / B ≦ 3.00 (1)

  If the ratio (A / B) is large, the transparent sheet has sufficient strength and can absorb the stress of shrinkage. Therefore, even if the water permeability and moisture permeability of the transparent sheet are low, cracking hardly occurs. Depending on the purpose of use of the recorded matter, the thickness of the transparent sheet as the protective layer may need to be several tens of μm or more from the viewpoint of long-term storage stability, weather resistance, and security. In this case, in consideration of the adhesive force between the image support of the recorded material and the color material receiving layer of the transfer material and the adhesive force between the color material receiving layer and the transparent sheet, a color containing a water-soluble resin is used. Depending on the degree of water absorption expansion and drying shrinkage of the material receiving layer, pores are provided in the transparent sheet to relieve stress. For example, when the transparent sheet is thick, the pore diameter is reduced or the pore distribution density is reduced. On the other hand, if the ratio (A / B) is small, the thickness of the transparent sheet becomes thinner than the thickness of the colorant receiving layer, and cracking of the transparent sheet is likely to occur, so that the water permeability and moisture permeability of the transparent sheet are increased. .

  Practically, the thickness of the transparent sheet is preferably 1 to 40 μm. By setting the thickness of the transparent sheet to 5 μm or more, the water resistance and scratch resistance of the transparent sheet can be further improved. On the other hand, if the thickness of the transparent sheet becomes too thick, a large amount of energy is required for heat transfer when the transparent sheet and the colorant receiving layer are thermocompression bonded to the image support. Further, in the drying after the immersion water resistance test, it is difficult for the water from evaporating from the colorant receiving layer through the pores of the transparent sheet, so that the thickness is preferably 40 μm or less. More preferably, by setting the thickness of the transparent sheet to 20 μm or less, in addition to the transparency and protection functions that are the basic functions of the transparent sheet, additional functions such as energy during thermocompression bonding and moisture permeability are provided. It becomes easy to obtain a balance.

[1-2-3] Pore Distribution Density The pore distribution density of the transparent sheet is not particularly limited, but is preferably 5 to 2 million per 1 cm ² . By setting it to 5 or more per 1 cm ^2, it is possible to evaporate an amount of water almost necessary for stress dispersion from the surface of the transparent sheet. Moreover, the intensity | strength and transparency of a transparent sheet can be maintained by making it 2 million or less.

  The degree of moisture permeation can be controlled not only by the average diameter of the pores in the transparent sheet but also by the distribution density, and cracks can be further suppressed. According to the study of the present inventor, the transparent sheet does not have a pore structure, and cracking occurs only by evaporating the water absorption component from the end portion. On the other hand, when pores were provided at intervals of 5 mm over the entire surface of the transparent sheet, fine streaks of streaks were observed on the surface of the dried transparent sheet, and no cracks were generated. When pores were provided at intervals of 2 mm over the entire surface of the transparent sheet, even fine wrinkle marks did not appear on the surface of the transparent sheet after drying, and the water resistance of the recorded material was ensured.

That is, in a configuration in which a transparent sheet having a thickness of about 10 μm is provided as a protective layer on a gap absorption type color material transfer layer having a thickness of about 20 μm, the fineness of the transparent sheet is provided so as to provide one or more pores per 4 mm 2. Cracks could be prevented by setting the distribution density of the holes. In addition, under normal circumstances, the transferred material evaporates and dries the absorbed water in about 30 minutes. Therefore, if the water vapor transmission rate of the transparent sheet is 5 g / m ² · h or more, the transfer material has water resistance. It can be improved further. That is, by setting the water vapor transmission rate of the transparent sheet to the above value or more, the stress when the colorant receiving layer after water absorption contracts is more widely dispersed, and cracking can be further prevented.

[1-2-3-2] Area of pores The total pore area on the surface of the transparent sheet is not particularly limited. The ratio (C / D) of the total pore area (C) of the transparent sheet surface to the total area (D) of the color material receiving layer at the edge, ie, evaporation from the edge of the color material receiving layer and from the transparent sheet surface It represents the rate of evaporation. The total pore area of the transparent sheet surface may be controlled so that C / D is preferably 0.02 to 50 times, more preferably 0.1 to 10 times, and even more preferably 0.2 to 5 times. preferable. C / D is preferably 0.02 times or more, more preferably 0.1 times or more, and even more preferably 0.2 times or more, thereby increasing the rate of moisture evaporation from the transparent sheet surface, It is possible to prevent cracking by suppressing the stress concentration due to evaporation of the. Further, the C / D is preferably 50 times or less, more preferably 10 times or less, and even more preferably 5 times or less, thereby suppressing a decrease in strength of the transparent sheet and improving scratch resistance. . On the other hand, if it becomes 0.02 times or less, the rate of evaporation from the end portion increases, the stress is not sufficiently dispersed, and cracks may occur. Furthermore, when it becomes 50 times or more, the strength of the transparent sheet is lowered, and the scratch resistance may be lowered.

  When liquid dirt such as contaminated water adheres to the surface of the transparent sheet, the contaminated water 552 passes through the pores 52A of the transparent sheet 52 as shown in FIG. May be absorbed by contact. In this case, a part of the information recorded by the reverse image 72 may be colored by the contaminated water 552 from the background side, and a part of the information may disappear. The transparent sheet is formed on the surface of the recorded material for the purpose of protecting the recorded material, and the protection performance can be roughly divided into the following four (1) to (4). (1) Protection performance against liquid dirt such as water, chemicals, and contaminated water, (2) Protection performance against gaseous dirt such as ozone and polluted gas, and (3) Optical such as ultraviolet light (4) is a protection performance against mechanical forces such as rubbing, scratching and hammering. About protection performance (2), (3), (4), it does not change a lot by the pore of a transparent sheet. However, when the pores of the transparent sheet are permeable to moisture, the protection performance from (1) liquid stains may be slightly reduced.

  Preferably, as shown in FIG. 35B, the pores 52A of the transparent sheet 52 are configured to have moisture permeability and moisture permeability. Thereby, although the water vapor | steam 550 lets the transparent sheet 52 pass, it becomes difficult to let liquid water, a chemical | medical agent, liquid dirt (contaminated water 552), etc. pass. Therefore, even if the contaminated water 552 adheres to the surface of the transparent sheet 52, it does not reach the color material receiving layer 53, the recorded information is protected from liquid stains, and the original protective function of the transparent sheet is There is no risk of damage. Furthermore, since the transparent sheet 52 allows water vapor to pass therethrough due to the moisture permeability of the pores 52A, even if the color material receiving layer 53 is dried after absorbing a large amount of water, the color material is received on the entire surface of the transparent sheet 52. The stress of the shrinkage of the layer 53 can be dispersed to suppress the occurrence of cracks. In this way, by providing moisture permeability to the pores of the transparent sheet, the original protective performance of the transparent sheet is prevented by preventing the entry of liquid dirt such as water, chemicals, and contaminated water from the surface of the transparent sheet. It is possible to suppress cracking by keeping the pores and providing the pores with moisture permeability.

  The moisture permeability and moisture permeability of the transparent sheet having pores are mainly controlled by the average diameter of the pores. By setting the average diameter of the pores of the transparent sheet to 0.001 to 0.8000 μm, it is possible to prevent cracking of the transparent sheet without impairing the protection performance against liquid stains on the colorant receiving layer. The size of the water droplet is about 100 μm, and a pore having a diameter of about several tens of μm usually forms a meniscus due to the surface tension of water at the tip, so that it is difficult for moisture to permeate. However, depending on conditions such as the action of pressure, wettability of the inner surface of the pores, and capillary force, moisture may permeate through pores having a diameter of about 1 μm. Therefore, by setting the average diameter of the pores to 0.8000 μm or less, it is possible to ensure sufficient moisture permeability and suppress the transmission of substantially liquid moisture. In addition, since the ease of moisture permeation changes depending on environmental conditions such as temperature, humidity and pressure, and viscosity and surface tension due to impurities and dissolved components contained in water, the average diameter of the pores is 0.2000 μm or less. As a result, practically sufficient moisture permeability can be obtained. On the other hand, considering the water molecule size of the water vapor, if the average diameter of the pores is 0.0004 μm or more, water vapor can be transmitted, and if the average diameter is 0.001 μm or more, it is sufficiently practical. A certain moisture permeability can be obtained. More preferably, in consideration of the uniformity of the pore structure, water vapor can be stably transmitted by setting the average diameter of the pores to 0.002 μm or more.

  Therefore, by setting the average diameter of the pores of the transparent sheet to 0.002 to 0.2000 μm, the moisture permeability is sufficiently suppressed while the cracks of the transparent sheet are sufficiently suppressed, and the surface dirt protection performance is actually used. It can be raised to a level where there is no problem. However, liquid stains may enter from the end of the colorant receiving layer. However, due to the difference in the degree of permeation and diffusion of the contaminated water component in each transfer material, the range in which the contaminated component permeates does not reach several mm from the end. In addition, from the viewpoint of mechanical restrictions such as the conveyance accuracy of the recorded matter, recording of information on the end portion of the recording unit is rare, and therefore, in actual use, information is not lost due to liquid contamination.

[1-2-4] Emulsion The transparent sheet 52 of this example contains two types of emulsions (emulsion E1 and emulsion E2) having different glass transition temperatures. Hereinafter, the emulsions E1 and E2 will be described in more detail.

[1-2-4-1] Emulsion State It is preferable that the emulsion E1 forms a film and at least the emulsion E2 remains as particles. The “film-forming state” of the emulsion means that it has been heat-treated at a temperature equal to or higher than the glass transition temperature. On the other hand, the “particle state” of the emulsion means that the heat treatment at a temperature higher than the glass transition temperature has not been performed. By setting the drying temperature after the emulsion coating to the glass transition temperature Tg1 or higher of the emulsion E1 and the glass transition temperature Tg2 or lower of the emulsion E2, the emulsion E1 forms a film and at least the emulsion E2 remains as particles. Can be manufactured. With this configuration, as shown in FIG. 71, the transparent sheet portion 980 of the portion 963 where the image support 55 and the color material receiving layer are bonded to each other and the image support and the color material receiving layer are bonded to each other at the time of thermocompression bonding. It can be controlled so that the film state is different between the transparent sheet portion 981 of the portion 964 that is not. That is, at the time of thermocompression bonding, since the heat of the heat roll is easily transmitted to the transparent sheet portion 980, a part of the emulsion E2 is formed into a film and some particles remain (FIG. 71), or the emulsion E2 of the transparent sheet is completely In this state, a film is formed (FIG. 71). At this time, the emulsion E2 that is partially or completely formed into a film can strengthen the bonding strength with the emulsion E1 that has been formed into a film in advance, thereby enhancing the film strength of the transparent sheet. On the other hand, since the heat of the heat roll is not transmitted to the transparent sheet portion 981, the emulsion E2 can be left in a particle state. Since the film state is different between the transparent sheet portion 980 and the transparent sheet portion 981, cracks are easily generated in the peeling step with the boundary portion 982 as a base point. As described above, the foil breakage can be improved by using two types of emulsions and changing the film state of the emulsion E2 using the temperature at the time of thermocompression bonding.

[1-2-4-2] Glass Transition Temperature of Emulsion Glass transition temperature (Tg) means that when an amorphous solid is heated, it is hard like a crystal at low temperatures (high rigidity) and has no fluidity. In addition, solids (viscosity was so large that they could not be measured) are temperatures at which rigidity and viscosity rapidly decrease and fluidity increases in a narrow temperature range. The glass transition temperature Tg is calculated from the Fox equation based on the glass transition temperature (Tg) of the homopolymer of each monomer and the mass fraction (copolymerization ratio based on mass) of the monomer. Is the value to be

  In this example, the unit of the numerical value representing the glass transition temperature is “° C.” unless otherwise specified. For example, the glass transition temperature of a copolymer composed of three types of monomers abc can be obtained by the following formula (9).

1 / Tg = Wa / Tga + Wb / Tgb + Wc / Tgc (9)
Tga, Tgb, Tgc: Glass transition temperature of homopolymer of each abc monomer W: Weight of each monomer Tg: Glass transition temperature of copolymer

  As the Tg of the homopolymer, the value described in known materials is adopted. In the technique disclosed here, the following values are specifically used as the Tg of the homopolymer.

2-Ethylhexyl acrylate -70 ° C
n-Butyl acrylate -55 ° C
Ethyl acrylate -22 ° C
Methyl acrylate 8 ℃
Methyl methacrylate 105 ° C
Isobornyl acrylate 94 ° C
Isobornyl methacrylate 180 ° C
Vinyl acetate 32 ° C
2-hydroxyethyl acrylate -15 ° C
Styrene 100 ° C
Acrylic acid 106 ℃
Methacrylic acid 130 ° C

  For the Tg of homopolymers other than those exemplified above, the values described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc, 1989) are used. When not described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989), values obtained by the following measurement method are used (Japanese Patent Laid-Open No. 2007-51271). reference).

[1-2-4-3] Emulsion E1
In this example, the emulsion E1 is in a film-forming state when the transparent sheet is formed. By forming the emulsion E1 into a film, the contact area with the colorant receiving layer can be increased. As a result, the adhesiveness between the transparent sheet and the colorant receiving layer is improved, and it can be controlled so that it does not peel off between the transparent sheet (protective layer) and the colorant receiving layer in tests such as tape peeling.

[1-2-4-4] Tg of emulsion E1
The glass transition temperature Tg1 of the emulsion E1 is greater than 50 ° C. and less than 90 ° C. Tg1 is more preferably greater than 55 ° C and less than 80 ° C, and even more preferably greater than 55 ° C and less than 70 ° C. By making Tg1 larger than 50 ° C., more preferably larger than 55 ° C., the glass transition temperature of the emulsion E1 becomes high, and the film portion of the transparent sheet becomes hard and hardly stretched. Therefore, when the end portion is cut, the film is prevented from extending, and the end portion can be kept clean, so that the end portion is cut. In addition, by controlling Tg1 within the above range, the resin is less likely to become familiar with oils and sweat of the hand, and the stretchability of the film is suppressed, so that even if the transparent sheet is touched by the hand, the transparent sheet is There is also an effect of suppressing stickiness of the transparent sheet. Further, when Tg1 is increased, the force acting between the molecular chains of the emulsion resin is increased, and it becomes difficult to dissolve in chemicals such as alcohol, so that the chemical resistance of the recorded matter can be remarkably improved. On the other hand, it is preferably less than 90 ° C., more preferably less than 80 ° C., and even more preferably less than 70 ° C., so that the film formation at the time of forming the transparent sheet can be easily performed. Adhesiveness can be improved. Furthermore, the brittleness of the film can be improved to prevent the transparent sheet from peeling off in the water resistance test. Moreover, it is difficult to keep the drying temperature completely constant in the actual manufacturing process, and a certain range can be achieved. When there is a range of drying temperatures, if Tg1 and Tg2 are close to each other, excessive heat is applied when E1 is formed into a film, the drying temperature exceeds Tg2, and it is difficult to maintain the particle state of E2. There is a case. Therefore, Tg1 and Tg2 satisfy the relationship of the following formula (13), and there is a difference of about 10 ° C. between Tg2 and Tg1, so that even when there is a range in drying temperature, excessive heat is not applied. Is preferable because the film and E2 can easily maintain the particle state. When Tg1 is 50 ° C. or lower, the resin becomes familiar with the oils and sweat of the hands, and stickiness tends to occur. Further, blocking is also likely to occur when the roll is formed. When Tg1 is 90 ° C. or higher, since E1 is difficult to form a film, the adhesiveness between the transparent sheet and the colorant-receiving layer is lowered, and the transparent sheet is easily peeled off. Furthermore, the film becomes brittle, and the transparent sheet peels easily in the water resistance test.
Tg2−Tg1 ≧ 10 (13)

[1-2-4-5] SP Value of Emulsion E1 Also, the difference ΔSP between the SP value of emulsion E1 and the SP value of the water-soluble resin of the colorant receiving layer is in the range of the following formula (1). Is preferred. By setting the difference ΔSP in such a range, the emulsion E1 becomes more compatible with the water-soluble resin during thermocompression bonding, and the intermolecular distance between the film-formed emulsion E1 and the water-soluble resin of the colorant receiving layer. Becomes shorter. Therefore, they can be strongly bonded by intermolecular forces composed of hydrogen bonds, van der Waals forces, etc., and the adhesion between the transparent sheet and the colorant receiving layer can be improved. When the difference ΔSP is larger than 0.6, the compatibility is lowered, the intermolecular distance between the filmed emulsion E1 and the water-soluble resin is increased, the intermolecular force is lowered, and the adhesive force is lowered, which is not preferable. .
0 ≦ | ΔSP | ≦ 0.6 (1)

[1-2-4-6] Material of Emulsion E1 As the material of emulsion E1, the acrylic resin, vinyl acetate resin, vinyl chloride resin, ethylene / vinyl acetate copolymer resin, polyamide resin, polyester resin, polyurethane resin, A resin such as a polyolefin resin or a copolymer resin thereof is preferable. Among these, acrylic resins can be formed at relatively low temperatures, have high transparency of the coating film, and have an SP value close to saponified polyvinyl alcohol contained as a water-soluble resin, improving adhesion. Therefore, it is particularly preferably used.

  As the acrylic resin, (meth) acrylic acid ester alone or a copolymer using the same can be used. Specific examples of (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acrylic acid-n. -Hexyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like. These (meth) acrylic acid esters can be used alone or in combination. Furthermore, these monomers that can be copolymerized with (meth) acrylic acid esters can be used after additional polymerization. Examples of such monomers include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid. Unsaturated carboxylic acids such as acid and itaconic acid; hydroxylethyl (meth) acrylate, hydroxylpropyl (meth) acrylate, (meth) acrylic acid (4) hydroxyl groups such as hydroxylbutyl described in JP-A-2002-121515 A monomer having an alkoxy group such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; a monomer having a glycidyl group such as glycidyl (meth) acrylate and allyl glycidyl ether Monomer having a (meth) acrylonitrile nitrile group; styrene, phenyl (meth) acrylate, Monomers having an aromatic ring such as meth) benzyl acrylate; monomers having an amide group such as (meth) acrylamide; monomers having an N-alkoxy group, N-methoxymethyl (meth) acrylamide, N- Monomers having an N-alkoxyalkyl group such as methoxyethyl (meth) acrylamide; Monomers having an N-alkylol group such as N-methylol (meth) acrylamide and N-butyrol (meth) acrylamide; Vinyl chloride , Monomers having a group to which halogen atoms are bonded, such as vinyl bromide, allyl chloride, 2-chloroethyl (meth) acrylate, chloromethylstyrene, vinyl fluoride; olefin monomers such as ethylene, propylene, butadiene, etc. Can be mentioned. It is also possible to partially crosslink using the reactive group of the material shown above.

  The emulsion used in this embodiment can be synthesized by a well-known technique that is generally well known, and commercially available materials can also be used. The Tg of the resin used in the emulsion can be adjusted by changing the monomer component and its ratio. The emulsion E1 may be a single type of emulsion, or a plurality of emulsions may be blended.

[1-2-4-7] Emulsion E2
In this embodiment, the emulsion E2 is in a particle state when the transparent sheet is formed. By making the emulsion E2 into a particle state, it is possible to improve the edge cutability during transfer.

[1-2-4-8] Tg of Emulsion E2
The glass transition temperature Tg2 of the emulsion E2 is 90 ° C. or higher and 120 ° C. or lower. More preferably, it is 95-115 degreeC, More preferably, it is 100-110 degreeC. The glass transition temperature Tg of the emulsion is 90 ° C. or higher, more preferably 95 ° C. or higher, and even more preferably 100 ° C. or higher.

  With this range, as shown in FIG. 71, the transparent sheet portion 980 of the portion 963 where the image support 55 and the color material receiving layer are bonded to each other and the image support and the color material receiving layer are bonded to each other at the time of thermocompression bonding. It can be controlled so that the film state differs between the transparent sheet portion 981 of the portion 964 that is not. That is, at the time of thermocompression bonding, since the heat of the heat roll is easily transmitted to the transparent sheet portion 980, a part of the emulsion E2 is formed into a film and some particles remain (FIG. 71), or the emulsion E2 of the transparent sheet is completely In this state, a film is formed (FIG. 71). On the other hand, since the heat of the heat roll is not transmitted to the transparent sheet portion 981, the emulsion E2 can be left in a particle state. Thereby, in a peeling process, it becomes easy to enter a crack on the boundary part 982.

  Furthermore, by making it into the said range, since the resin of emulsion E2 becomes difficult to extend | expand and it becomes difficult to become familiar with fats and oils and sweat of a hand, the stickiness of a transparent sheet can be prevented. In addition, by making it in the above range, the solubility in chemicals such as alcohol is lowered, and the chemical resistance is improved. In addition, by setting the glass transition temperature Tg of the emulsion to 120 ° C. or lower, more preferably 115 ° C. or lower, and even more preferably 110 ° C. or lower, the thermal energy in thermocompression bonding can be controlled efficiently with low energy to support the image. Thermal deformation due to the addition of excessive heat energy to the body can be prevented. In the present invention, the colorant-receiving layer can be transferred to the image support by setting the water-soluble resin polyvinyl alcohol (PVA) of the colorant-receiving layer to a glass transition temperature of about 90 ° C. or higher. Therefore, within the above temperature range, when the colorant receiving layer is heated and pressure-bonded to the image support, the transparent sheet close to the heat roll side becomes Tg2 or higher in the process of heating the colorant receiving layer to about 90 ° C. Since it is heated, the emulsion E2 can be transferred into a film without giving excessive thermal energy during transfer. When Tg2 is smaller than 90 ° C., it becomes easy to become familiar with hand oils and fats and sweat, so that it becomes sticky and blocking properties are likely to occur. Furthermore, cracks are less likely to occur, and the foil breakability also decreases. When Tg2 is greater than 120, high energy is required for thermal compression in thermocompression bonding, and thermal deformation due to addition of excessive thermal energy to the image support tends to occur.

[1-2-4-9] Material of Emulsion E2 As the polymer substance constituting the emulsion E2, the same material as the emulsion E1 can be used. However, acrylic resins and urethane resins are preferably used because the SP difference SP1 between the transparent sheet and the base sheet can be controlled to 1.1 or more and the peelability from the base sheet is improved. Particularly preferred for the emulsion E2 is a urethane resin. By using urethane resin, it has moderate softness and stickiness is suppressed. Furthermore, the brittleness of the film and the solubility in chemicals are improved, and even when immersed in chemicals such as alcohol, cracking and peeling are less likely to occur, and chemical resistance can be improved. Emulsion E2 preferably uses a different type of resin from emulsion E1, and the use of different types of resin makes it difficult for the resins to be compatible with each other, making it easy to maintain the coexistence state of the film and particles before transfer. . When an acrylic resin is used as the emulsion E1, the urethane resin is particularly preferable as the emulsion E2.

  Examples of the urethane resin include urethane resins synthesized by a polyaddition reaction using various combinations of the following polyol compounds and diisocyanate compounds. The urethane resin is not particularly limited, but a polyether urethane resin synthesized from a polyether polyol compound and a diisocyanate compound is preferable. Since the polyether urethane resin is hardly hydrolyzed, the durability including the water resistance of the recorded matter is improved.

  As the polyol compound, any diol containing two hydroxyl groups or a polyol containing three or more hydroxyl groups can be used without particular limitation. For example, polyether, polyester, polycarbonate, acrylic, polybutadiene or polyolefin polyols, caprolactone modified polyol, polyester amide polyol, polyurethane polyol, epoxy polyol, epoxy modified polyol, alkyd modified polyol, castor oil, fluorine-containing Polyols such as polyols may be used alone or in combination.

  Specific examples of polyether polyols include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and ethylenediamine. Starting with compounds having at least two active hydrogen groups such as aliphatic amine compounds, aromatic amine compounds such as toluenediamine and diphenylmethane-4,4-diamine, and alkanolamines such as ethanolamine and diethanolamine It is obtained by adding an alkylene oxide typified by ethylene oxide, propylene oxide, butylene oxide or polyoxytetramethylene oxide as a raw material. Polyol, and the like.

  Specific examples of the polyester polyol include at least one selected from, for example, ethylene glycol, propylene glycol, butanediol pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. A condensation polymer of a seed and at least one selected from glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid, other low molecular weight aliphatic carboxylic acid and oligomeric acid; propionlactone or valerolactone Ring-opening polymers such as;

  Other polyols include, for example, polymer polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol Examples include molecular polyols.

  The diisocyanate compound can be used without any particular limitation. Diisocyanate compounds include methylene diisocyanate, ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,5. -Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenylene diisocyanate, 4,4'-biphenylene diisocyanate, dicyclohexylmethane diisocyanate, And methylene bis (4-cyclohexyl isocyanate).

[1-2-4-10] Average particle size of emulsion E2 The average particle size of emulsion E2 is not particularly limited, but is preferably 1 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 50 nm. is there. By setting the average particle size to preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more, the transparent sheet of the portion 964 where the image support and the colorant receiving layer are not adhered at the time of thermocompression bonding It becomes easy to make emulsion E2 into the particle state of the part 980. Therefore, cracks are likely to occur at the boundary between the transparent sheet portion 980 of the portion 963 where the image support 55 and the colorant receiving layer are bonded, and there is no occurrence of burrs at the edges in the peeling process after transfer. Cutting performance can be improved. In the transfer material of the present invention, since the emulsion E2 is maintained in a particle state, the particle size of the emulsion E2 greatly affects the transparency of the transparent sheet. By setting the average particle size of the emulsion E2 to 200 nm or less, more preferably 150 nm or less, and even more preferably 50 nm or less, the transparency of the transparent sheet can be improved. Furthermore, when the particle diameter is equal to or smaller than the above, fine cracks are likely to occur, and the edge cutability is also improved. If the average particle diameter of E2 is smaller than 1 nm, the particles are too small, so that the transparent sheet is close to a film, cracks are difficult to occur during transfer, and the foil breakage is reduced. If the average particle diameter of E2 is larger than 200 nm, the transparency may be lowered.

[1-2-4-11] Mixing ratio of emulsions E1 and E2 In the present invention, the ratio of emulsion E1 to emulsion E2 (E1 / E2) preferably satisfies the following formula (3), more preferably 5. It is preferable that 0 ≦ E1 / E2 ≦ 50.0, still more preferably 10.0 ≦ E1 / E2 ≦ 35.0. By setting E1 / E2 to 65.0 or less, more preferably 50.0 or less, more preferably 35.0 or less, E2 increases, and the particle component increases, so that emulsion E2 remains in a particle state. Is easy to crack, and cracks easily occur at the boundary between the image support 55 and the transparent sheet portion 980 of the portion 963 where the colorant receiving layer is adhered, and there is no occurrence of burrs at the end portion, resulting in the ability to break the foil. Can be good.

  That is, by setting this range, as shown in FIG. 71, the transparent sheet portion 980 of the portion 963 where the image support 55 and the color material receiving layer are bonded, and the image support and the color material receiving layer as shown in FIG. It can be controlled so that the film state is different between the transparent sheet portion 981 of the portion 964 where the film is not bonded. At the time of thermocompression bonding, since the heat of the heat roll is easily transmitted to the transparent sheet portion 980, a part of the emulsion E2 is formed into a film and a part of the particles remains (FIG. 40 (b)), or the emulsion E2 of the transparent sheet is formed. A completely filmed state (FIG. 40C) is obtained.

On the other hand, when E1 / E2 is 3.0 or more, more preferably 5.0 or more, and even more preferably 10.0 or more, E1 is increased, and the film-forming component is increased to improve the film strength. Furthermore, a contact area with a color material receiving layer becomes large, and the adhesiveness of a color material receiving layer and a transparent sheet can be improved. In particular, by setting the range of 10.0 ≦ E1 / E2 ≦ 35.0, it is possible to achieve both a high level of improvement in adhesiveness, edge cutability, and crack prevention. When E1 / E2 is larger than 65.0, the particle component is reduced and approaches the state of the film, so that it becomes difficult for cracks to occur and it becomes difficult to obtain the foil breakability. Further, when E1 / E2 is smaller than 3.0, since E1 serving as a binder for E2 is reduced, the emulsion of the transparent sheet may be peeled off or powdered off at the time of forming the colorant receiving layer. There is a possibility that the layer cannot be formed uniformly. Furthermore, since the film component is reduced, the adhesiveness with the colorant receiving layer is lowered and peeling of the transparent sheet is likely to occur.
3.0 ≦ E1 / E2 ≦ 65.0 (3)

  When the ratio of emulsions E1 and E2 (E1 / E2) is less than 10 (the ratio of emulsion E2 is more than 9.1%), the emulsion is used for the transparent sheet of the transfer material including the transparent sheet and the colorant receiving layer. When part of the film is formed into a film and partly in the form of particles, the colorant receiving layer applied to the transparent sheet cannot withstand the shrinkage caused by drying, and the transparent sheet is cracked. May be more likely to occur. This phenomenon is a phenomenon peculiar to the type of transfer material containing a color material receiving layer, and occurs only when an aqueous coating liquid containing a water-soluble compound and inorganic fine particles is applied on a transparent sheet. It does not occur with transfer materials that consist only of a substrate and a protective layer. In particular, in the case of a transfer material that is preferably used in an ink jet system as in the present invention, since it is necessary to absorb a large amount of ink in the color material receiving layer, the thickness of the color material receiving layer is increased, and the coating amount and the drying amount are increased. Since the amount of shrinkage at the time also increases, cracking during coating tends to occur. Further, in the case of using an emulsion resin E1 having a glass transition temperature Tg1 higher than 50 ° C. as an emulsion formed into a film in a transparent sheet in consideration of adhesiveness, whiteness, chemical resistance, and stickiness prevention as in the present invention. The emulsion resin is hard and difficult to stretch, and the phenomenon of cracking tends to occur very easily due to shrinkage. From the above, as in the present invention, the base material, the colorant receiving layer, and the transparent sheet are sequentially laminated, and the transparent sheet contains the emulsions E1 and E2, and the glass transition temperature Tg1 of the emulsion E1 formed into a film is 50 ° C. If the emulsion E2 remains larger as particles, it is important to precisely control the ratio of E1 and E2.

When the transparent sheet of the present embodiment abuts on the base sheet, those materials are set so that the absolute value | SP1 | of the difference between the SP value of the base sheet and the SP value of the transparent sheet satisfies the following expression (10). Is preferably selected. When the absolute value | SP1 | of the difference satisfies the relationship of the following expression (10), the transparent sheet and the base sheet are laminated with a relatively weak adhesive state. Thereby, at the time of transfer, the base material sheet is easily peeled off from the transparent sheet, and on the other hand, the adhesion between the colorant receiving layer and the image support can be strengthened, so that the transferability at the time of transfer is improved. Can do.
1.1 ≦ | SP1 | ≦ 3 (10)

  In addition, the image recorded on the colorant receiving layer is visually recognized as an original image through the transparent sheet by heat-pressing the transfer material of the present embodiment to the image support and peeling the base sheet. Can do. Further, when the transfer material is heat-pressed to the image support, the transparent sheet functions as a protective layer for the image recorded on the color material receiving layer.

  The transparent sheet is a sheet having a total light transmittance measured in accordance with JIS K7375 of 50% or more, preferably 90% or more. Accordingly, the transparent sheet includes a semi-transparent sheet and a colored transparent sheet in addition to the colorless transparent sheet. When a dye ink is used as an ink for recording an image on the colorant-receiving layer, the transparent sheet preferably contains a UV cut agent in order to prevent the dye from being decomposed (photodegraded) by ultraviolet rays. Examples of the UV-cutting agent include ultraviolet absorbers such as benzotriazole compounds and benzophenone compounds; ultraviolet scattering agents such as titanium oxide and zinc oxide;

[1-2-5] Method for forming pores When the transparent sheet is mainly composed of a resin and is formed on a substrate sheet, there are various methods for forming pores in the transparent sheet. This method can be applied. For example, in the film forming process of the transparent sheet or in the subsequent process, the pores of the open cell structure are configured as shown in FIGS. 36, 37, and 38 by the components contained in the constituent material of the transparent sheet. You may do it. As will be described later, in FIG. 36, FIG. 37, and FIG. 38, pores having an open cell structure are formed using a foaming agent, porous particles, and hollow particles, respectively. Further, as shown in FIGS. 39 and 40, a transparent sheet having a pore structure may be prepared in advance, and may be laminated or laminated and adhered on the base sheet. Details thereof will be described later. Furthermore, as shown in FIG. 41 and FIG. 42, after forming a transparent sheet on a base sheet, a pore treatment for forming desired pores in the transparent sheet may be performed by another means. Details thereof will be described later. Thus, the pores of the transparent sheet need only have a pore structure that penetrates between the base material sheet and the colorant receiving layer, and can be formed using a known method. The optimum forming method can be selected according to the application.

[1-2-6] Foaming agent In the case of forming a continuous cell structure in a transparent sheet using a foaming agent, mechanical stirring is applied to the coating solution containing the emulsion, Fine bubbles are formed and dispersed to form a transparent sheet.

  Specifically, as shown in FIG. 36, the coating liquid containing the emulsion is stirred to prepare a coating liquid in which a large number of fine bubbles 553 are dispersed, and the coating liquid is prepared using a die coater 655A. Then, a thin transparent sheet 52 is formed. In the case of FIG. 36A, after forming the color material receiving layer 53 on the transparent sheet 52 using the die coater 655B, the reference sheet 50 is formed using the die coater 65C. In the case of FIG. 36B, after the reference sheet 50 is formed on the transparent sheet 52 using the die coater 65C, the color material receiving layer 53 is formed using the die coater 655B. In the case of FIG. 36C, the transparent sheet 52 is formed on the reference sheet 50 prepared in advance using the die coater 655A, and then the color material receiving layer 53 is formed using the die coater 655B. As a result, as shown in FIG. 20F, the transfer material 1 including the transparent sheet 52 having the continuous bubble structure in which the bubbles 553 are continuous is manufactured.

  The mechanical stirring method of the coating liquid for forming the transparent sheet 52 is not particularly limited, and is a foaming machine having a known stirring blade, a homomixer used for emulsification dispersion, etc., a stirring machine such as a cowless dissolver, and the like. It can be performed using a continuous foaming machine or the like. In order to stabilize the film-forming property by foaming, it is desirable to add a resin to the coating liquid containing the emulsion. As the resin, those equivalent to the water-soluble resin added to the colorant receiving layer can be used, but are not limited thereto. These resins can be used alone or in combination of two or more as required.

  In such a coating liquid containing an emulsion and a resin, in order to improve the stability of the bubbles, a material having a surface active action called a foam stabilizer or a foaming agent is appropriately selected and blended. Also good. For example, by paying out anionic surfactants such as higher fatty acids, higher fatty acid modified products, higher aliphatic alkali salts, higher fatty acid amine salts, etc. The stability of bubbles can be increased. The material of these foam stabilizers or foaming agents is not limited, and can be selected in consideration of the fluidity of the resin liquid and the coating workability.

  The blending ratio of the foam stabilizer or the foaming agent to the resin liquid is preferably 0 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the solid content of the resin liquid. . If the blending ratio exceeds 30 parts by weight, many bubbles can be controlled to be small, but the transparency of the transparent sheet produced by the bubbles is lowered and the visibility of the recorded image is lowered, which is not preferable.

  Moreover, regarding the coating liquid containing the emulsion and the resin, the volume ratio of the volume after foaming to the volume before foaming (hereinafter referred to as foaming ratio) may be set in consideration of the balance with the composition of the resin liquid. The expansion ratio is preferably more than 0.5 times and not more than 10 times, more preferably not less than 1.0 times and not more than 5 times. The expansion ratio is a scale indicating the bubble content in the coating liquid of the water-dispersed resin containing bubbles. When the expansion ratio is 0.5 times or less, it is difficult to obtain a sufficient open cell structure for the transparent sheet to exhibit moisture permeability or moisture permeability, which is not preferable. On the other hand, if the expansion ratio is 10 times or more, the thickness of the resin liquid film (wall) constituting the bubbles becomes thin, and the function as a protective layer other than water resistance is lowered, which is not preferable. In that case, the amount of air to be included increases and the heat insulating property of the transparent sheet becomes high, and there is a possibility that the transfer performance is lowered. Furthermore, since the resin film (wall) surrounding the pores of the pore-containing resin layer becomes thinner as the solid content concentration of the water-dispersed resin liquid before foaming is lower, the function as a protective layer is lowered.

[1-2-7] Porous particles When the open cell structure is formed in the transparent sheet using the porous particles, a transparent sheet mainly composed of a resin containing porous particles is formed on the base sheet. Film formation is performed, and pores penetrating between the base material sheet and the colorant receiving layer are formed by connecting the porous particles. For example, as shown in FIG. 37, a transparent sheet 52 is formed from a resin material containing porous particles 554 using a die coater 655A.

  In the case of FIG. 37 (a), the colorant receiving layer 53 is formed on the transparent sheet 52 using the die coater 655B, and then the reference sheet 50 is formed using the die coater 65C. In the case of FIG. 37B, the reference sheet 50 is formed on the transparent sheet 52 using the die coater 65C, and then the colorant receiving layer 53 is formed using the die coater 655B. In the case of FIG. 37 (c), the transparent sheet 52 is formed on the reference sheet 50 prepared in advance using the die coater 655A, and then the color material receiving layer 53 is formed using the die coater 655B. As a result, as shown in FIG. 22G, the transfer material 1 including the transparent sheet 52 having the open cell structure in which the porous portions of the porous particles 554 are continuous is manufactured.

  The material of the porous particles is not particularly limited, and both organic and inorganic materials can be used. However, it is preferable to use porous inorganic fine particles from the viewpoint of heat resistance. For example, calcium carbonate, magnesium carbonate, kaolin, clay, talc, hydrotalcite, aluminum silicate, calcium silicate, magnesium silicate, diatomaceous earth, alumina, colloidal alumina, aluminum hydroxide, boehmite structure alumina hydrate, pseudo boehmite structure And alumina hydrate, lithopone (a mixture of barium sulfate and zinc sulfide), zeolite and the like. The density of the pores can be controlled according to the content of the porous particles. The content of the porous particles is preferably about 1% to 30% with respect to the total amount of the emulsion. When the content is 1% or less, the water permeability is lowered and cracking is likely to occur. If it is 30% or more, the water permeability increases, the liquid is excessively absorbed, and the protective performance as a transparent sheet is lowered.

[1-2-8] Hollow resin particles When the open cell structure is formed in the transparent sheet using the hollow particles, a transparent sheet mainly composed of a resin containing hollow particles is formed on the base sheet. Then, pores penetrating between the base material sheet and the colorant receiving layer are formed by the connection of the hollow particles. For example, as shown in FIG. 38, a transparent sheet 52 is formed from a resin material containing hollow particles 555 using a die coater 655A.

  In the case of FIG. 38A, after forming the color material receiving layer 53 on the transparent sheet 52 using the die coater 655B, the reference sheet 50 is formed using the die coater 65C. In the case of FIG. 38B, the reference sheet 50 is formed on the transparent sheet 52 using the die coater 65C, and then the colorant receiving layer 53 is formed using the die coater 655B. In the case of FIG. 38C, the transparent sheet 52 is formed on the reference sheet 50 prepared in advance using the die coater 655A, and then the color material receiving layer 53 is formed using the die coater 655B. As a result, as shown in FIG. 22 (h), the transfer material 1 including the transparent sheet 52 having the open cell structure in which the hollow portions of the hollow particles 555 are continuous is manufactured.

  The material of the hollow resin particles is not particularly limited, and both organic and inorganic materials can be used. However, it is preferable to use hollow inorganic fine particles from the viewpoint of heat resistance. Examples thereof include glass, shirasu, silica, alumina, and ceramic. The density of the pores can be controlled according to the content of the hollow particles. The content of the hollow particles is preferably about 1% to 30% with respect to the total amount of the emulsion. If it is 1% or less, the water permeability decreases and cracking is likely to occur. When it becomes 30% or more, the water permeability increases, the liquid is excessively absorbed, and the protective performance as a transparent sheet is lowered.

The material of the hollow particles is not particularly limited, and both inorganic and organic materials can be used. The hollow inorganic fine particles are excellent in heat resistance, and for example, glass, shirasu, silica, alumina, ceramic and the like can be used. There are several types of hollow resin fine particles depending on the production method, and examples thereof include the following methods (1) to (5).
(1) A method in which a foaming agent is contained in polymer particles, and this is subsequently foamed to obtain hollow particles.
(2) A method in which a volatile substance such as butane is encapsulated in a polymer, which is then gasified and expanded to obtain hollow particles.
(3) A method in which a polymer is melted, a jet of air or the like is sprayed thereon, and bubbles are enclosed.
(4) A method in which a polymerizable monomer component is dispersed in water to form an oil-in-water emulsion and polymerized to obtain hollow particles.
(5) A method in which an alkali-swellable substance is contained in the polymer particles, and an alkaline liquid is infiltrated into the polymer particles to expand the alkali-swellable substance to obtain hollow particles.

  When hollow resin particles are used to form pores that allow the colorant-receiving layer to communicate with the atmosphere in the base sheet and the transparent sheet, the pores must have a continuous cell structure. The hollow particles used for this purpose are preferably those having fine holes in the shell, and among the above (1) to (5), hollow particles produced by the method (4) or (5) are preferred. The hollow particles produced by the above (1) to (3) do not have fine holes in the shell, and are difficult to release water out of the system when placed in a transparent sheet. The density of the pores can be controlled according to the content of the hollow particles. The content of the hollow particles is preferably about 1% to 30% with respect to the total amount of the emulsion. If it is 1% or less, the water permeability decreases and cracking is likely to occur. If it becomes 30% or more, the amount of air contained in the voids increases, the heat insulating property of the base sheet becomes high, and the transfer performance may be lowered.

[1-2-9] Stretching Treatment A film having a pore structure in advance may be used as the transparent film, and pores can be formed on the film by subjecting it to a stretching treatment. For example, as illustrated in FIG. 43, the pores 521 can be formed by stretching a film that is a material of the transparent sheet 52 by a stretching apparatus 656.

As the film for the transparent sheet 52, a waterproof and moisture permeable film produced by combining an ePTFE film obtained by stretching polytetrafluoroethylene (PTFE) and a polyurethane polymer can be used. In this case, 1.4 billion fine holes can be formed in one square centimeter to achieve both waterproofness and moisture permeability. Its water pressure resistance of the film is 45000mm above, moisture permeability is 13500g / m ² / 24hrs as measured in JIS L1099B-2 method. Such a film can be used as a single layer, or may be used as a multilayer with other water-permeable films, and can be laminated on a base sheet as a transparent sheet. That is, any transparent film having a pore structure penetrating the front and back can be used as a transparent sheet for a transfer material. As the film, it is possible to use a porous film obtained by stretching a film in which calcium carbonate is dispersed with polyethylene as a main component, and a porous film having a polyolefin as a main component and stretched without an inorganic filler. it can. Since these films can provide a stable pore structure, it can be used as a water-permeable or waterproof moisture-permeable transparent sheet.

[1-2-10] Crazing treatment The processing method for forming the pore structure in the resin film is not limited to the above-described stretching treatment, and crazing may be used.

  For example, a pore structure can be formed in the resin film using a crazing apparatus 651 as shown in FIG. In other words, a transparent polyvinylidene fluoride film, that is, a film as a material of the transparent sheet 52, is bent at a predetermined angle 652 substantially in parallel with the molecular orientation direction by the craze processing unit 653, and pressure is applied to the upper and lower surfaces thereof. While pulling in the direction of arrow a. Thereby, in the film as the material of the transparent sheet 52, as shown in FIG. 45 (a), striped crazes forming a fine continuous cracked pattern are formed substantially parallel to the molecular orientation direction, The crazes form pores 52A. As shown in FIG. 45 (b), when the base sheet 50 is bonded to the film that is the material of the transparent sheet 52 and then subjected to crazing treatment, the pores 52A and 40A are formed. In addition, as shown in FIG. 45 (c), when the base material sheet 50 and the colorant receiving layer 53 are bonded to a film that is a material of the transparent sheet 52 and then subjected to a craze treatment, the pores 52A, 40A and 53A are formed.

  The craze includes a surface craze that appears on the surface of the resin film and an internal craze that is generated inside. The transparent sheet 52 may be formed by connecting these crazes to form the pores 52 </ b> A penetrating the transparent sheet 52. In other words, molecular bundles (fibrils) and pores (voids) are formed in the film for the transparent sheet 52 by craze processing, and these are partially connected to each other so as to form a sponge structure as a whole. 52A may be formed. The film in which such pores 52A are formed can be used as a water-permeable or moisture-proof and moisture-permeable transparent sheet 52. In addition, the craze may be lost by being relaxed by heat treatment or the like. However, since it appears again by being pulled again, the pore structure of the transparent sheet 52 can be adjusted by laminating it on the base sheet 50 while applying an appropriate tension to the crazed transparent sheet 52. Further, the size of the pores 52A can be adjusted by the force of pulling the film during craze processing, the pressure applied to the upper and lower surfaces of the film, and the like. In addition, a pore structure can be formed by craze processing a polyvinylidene fluoride film. For example, films of polystyrene, polyethylene, polypropylene, polyester, polyamide, and the like can be used.

《Pore treatment after forming transparent sheet》
[1-2-11] Perforation Processing When the transparent sheet 52 does not have a pore structure as shown in FIG. 1B, the pores 52A can be formed in the transparent sheet 52 by various perforation processes. . As the drilling process, mechanical drilling such as a needle 657, a spur 650, and a blade shape as shown in FIGS. 46A and 46B, or laser processing using a laser processing device 658 as shown in FIG. 46C is performed. Can be used.

  After perforating the transparent sheet 52 as shown in FIG. 39, the base sheet 50 and the color material transfer layer 53 may be laminated on the transparent sheet 52 as shown in FIG. Good. Further, as shown in FIG. 40 (a) or (b), after laminating the transparent sheet 52 and the color material transfer layer 53, after performing a perforating process from the transparent sheet 52 side or the color material transfer layer 53 side, The base sheet 50 may be laminated. In addition, after laminating the transparent sheet 52 and the base sheet 50 as shown in FIG. 41, a perforation process is performed as shown in FIGS. You may laminate. In the case of FIG. 41 (a), the transparent sheet 52 is punched, and in the case of FIG. 41 (b), the transparent sheet 52 and the base sheet 50 are punched from the transparent sheet 52 side. In this case, the transparent sheet 52 and the base sheet 50 are perforated from the base sheet 50 side. Further, after laminating the transparent sheet 52, the base material sheet 50, and the color material transfer layer 53 as shown in FIG. 42, the punching process is performed as shown in FIGS. 42 (a), (b), (c), and (d). You may give it. In the case of FIG. 42 (a), the transparent sheet 52 and the base sheet 50 are perforated from the base sheet 50 side, and in the case of FIG. 42 (b), the transparent sheet 52, the base sheet 50, and the color material transfer layer. 53 is perforated from the substrate sheet 50 side. In the case of FIG. 42 (c), the transparent sheet 52 and the color material transfer layer 53 are perforated from the color material transfer layer 53 side, and in the case of FIG. 42 (d), the transparent sheet 52, the base sheet 50, and the color material. The transfer layer 53 is perforated from the color material transfer layer 53 side.

  In the example of FIG. 42, a punching process is performed on the transfer material 1 before the reverse image 72 is formed. However, as shown in FIGS. 24 to 26, the reverse image 72 may be recorded on the transfer material 1 (step 1) and then the punching process may be performed. In the case of FIG. 24, the transfer material 1 on which the reverse image 72 is recorded is subjected to a punching process (a punching process) as shown in FIGS. The material transfer layer 53 is transferred to the recorded image support 55 (step 2), and the base sheet 50 is peeled off (step 3). In the case of FIG. 25, after transferring the color material transfer layer 53 to the image support 55 (step 2), the substrate sheet 50 is peeled off (step 3) after being subjected to perforation processing (perforation step). In the case of FIG. 26, the color material transfer layer 53 is transferred to the image support 55 (step 2), the substrate sheet 50 is peeled off (step 3), and then a perforation process (perforation step) is performed.

  Thus, at least before the recorded material is actually used, it is only necessary to form the pores 52A penetrating the transparent sheet 52 covering the surface.

[1-2-12] Drilling (needle)
As shown in FIGS. 46 (a) and 46 (b), as a simple processing method for imparting a pore structure to the transparent sheet, pores penetrating the transparent sheet by pressing a sharp-pointed needle or blade shape. There is a method of forming.

  When the transparent sheet is a thin resin film, it can be perforated by pressing with a small pressure. In the case of a slightly thick resin film, it is possible to give a more stable pore structure by performing mechanical perforation while the resin film is heated to around the glass transition temperature. By using a needle row, needle roller, spur row, blade shape, blade shape roll with sharply machined tips of metal, ceramics, etc., a suitable pore structure can be continuously provided and drilled efficiently. . Furthermore, the durability can be improved by applying diamond processing or the like to the sharp tip. As described above, the perforation processing of the transparent sheet is performed in the state of being laminated on the base material sheet, the state of being laminated with the color material receiving layer, or the base material sheet, the transparent sheet, and the color material receiving as well as the transparent sheet alone. It can carry out with respect to the transparent sheet in the state where the layers were sequentially laminated. If the transparent sheet is exposed on the surface, it is preferable to perform mechanical perforation from the surface side of the transparent sheet. When the transparent sheet is sandwiched between other layers such as a base sheet or a colorant receiving layer, the transparent sheet is inserted through the other layer side in consideration of mechanical strength such as the thickness and material of the other layer. What is necessary is just to perform the mechanical drilling which penetrates. In this case, fine pores are also formed in the base material sheet and the color material receiving layer. However, the diameter and density of the pores may be adjusted taking care not to affect the transferability of the transfer material and the inkjet recording characteristics.

  As described above, it is also possible to perforate the transparent sheet after the colorant receiving layer and the transparent sheet have been transferred to the image support. As described above, since it is preferable to perform mechanical perforation processing in a state where the transparent sheet is heated, mechanical perforation is performed immediately after the base material sheet is peeled off after heat-pressing the transfer material to the image support. It is preferable to perform processing. When punching is performed by a spur train having a sharp tip, the spur train can be provided with a function of conveying and discharging the image support. Similarly, when drilling is performed using spur trains, needle rollers, etc. during the film forming / laminating process of transparent sheets and transfer materials and in image recording devices, the spur trains, needle rollers, etc. It is possible to have a film transport function. As described above, the recorded material may be mechanically provided with a pore structure penetrating the transparent sheet, and the method and apparatus configuration are not particularly limited.

[1-2-13] Drilling (laser)
As shown in FIG. 46C, as a simple processing method for imparting a pore structure to the transparent sheet, there is a method using a laser processing apparatus 658.

  When the transparent sheet is a thin resin film, a well-known and stable pore structure can be imparted with high productivity using a known laser processing apparatus. For example, Japanese Patent Publication No. 2706498 describes a laser processing method in which the level of reflected laser light from the workpiece surface is detected and the processing proceeds to processing of the next pore, and this processing method is detailed on a transparent sheet. It can be applied as a method for imparting a pore structure. The hole diameter of the pores provided in the transparent sheet can be set by selecting the laser light source and adjusting the optical system such as the laser beam condenser lens, and the interval between the pores is set by the optical scanning system such as a reflection mirror Is possible. The drilling process by laser processing is the same as the mechanical drilling process, in addition to the transparent sheet alone, the state laminated on the base sheet, the state laminated with the colorant receiving layer, or the base sheet, transparent sheet, And the transparent sheet in which the colorant receiving layers are sequentially laminated. If the transparent sheet is exposed on the surface, it is preferable to perform perforation by irradiating laser light from the surface side of the transparent sheet. In addition, when the transparent sheet is sandwiched between other layers such as a base sheet or a colorant receiving layer, the light absorption characteristics of the transparent sheet and the optical characteristics such as the thickness and material of the other layers are considered. Then, the transparent sheet can be perforated by irradiating laser light from the other layer side. In this case, fine pores may be formed in the base material sheet and the colorant receiving layer. However, the diameter and density of the pores may be adjusted taking care not to affect the transferability of the transfer material and the ink jet recording characteristics. In addition, if necessary, a laser light reflection film or the like may be provided on the surface of the other layer opposite to the laser light irradiation side so that the transparent sheet can efficiently absorb the laser light. Good. In addition, fine particles that easily absorb laser light may be dispersed in the resin of the transparent sheet in advance to improve the drilling workability by laser light.

[1-3] Base Material Sheet The transfer material of this embodiment includes a base material sheet 50 as in the case of the transfer material 1 in FIG. A base sheet (also referred to as “release liner” or “separator”) is a sheet body that serves as a support for a release layer or a colorant receiving layer described later.

  As for the material of the base sheet, as described above, it is preferable that the difference SP1 between the SP value of the base sheet and the SP value of the colorant receiving layer satisfies the formula (10). Examples of the material include a resin film. For example, a resin film that has been used as a base film of a conventional thermal transfer sheet can be used as it is as the base sheet.

  Examples of the material for forming the base sheet include polyester (PET, etc.), nylon (aliphatic polyamide), polyimide, cellulose acetate, cellophane, polyethylene, polypropylene, polystyrene, polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, A resin film made of a resin such as chlorinated rubber, fluororesin, or ionomer is preferred. Among these, a PET film having excellent heat resistance is preferable. The resin film can be used alone or in combination of two or more.

  The thickness of the substrate sheet may be appropriately determined in consideration of material strength and the like, and is not particularly limited. However, the thickness of the base sheet is preferably 5 to 200 μm. By setting the thickness of the base sheet to preferably 5 μm or more, and more preferably 10 μm or more, curling of the laminate can be prevented when the colorant receiving layer is laminated. When the transfer material is in a roll shape, it is preferable that the thickness of the transfer material is 15 μm or more in order to improve transportability on the transfer material manufacturing apparatus. When the transfer material is cut sheet, the thickness of the transfer material is preferably 30 μm or more from the viewpoint of preventing curling of the cut sheet.

  On the other hand, when the thickness of the substrate sheet is 200 μm or less, preferably 60 μm or less, more preferably 50 μm or less, the heat transfer property when the transfer material is heat-pressed to the image support can be improved.

[1-4] Release Layer The transfer material may include a release layer 51 like the transfer material 1 in FIG. The release layer 51 is a layer made of a composition containing a release agent, and is provided between the base sheet 50 and the transparent sheet 52. By providing the release layer 51, the base sheet 50 can be easily peeled from the transparent sheet 52.

  The type of release agent is not particularly limited, and is preferably a material that is excellent in releasability and is not easily melted by heat generated by a heat roller or a thermal ink jet recording head. For example, silicone waxes typified by waxes such as silicone wax, silicone-based materials such as silicone resins, and fluorine-based materials such as fluororesins are preferable in terms of excellent releasability.

  The thickness of the release layer may be appropriately determined in consideration of peelability and the like, and is not particularly limited. However, the thickness of the release layer is preferably 0.1 to 10 μm in a dry state. By setting the thickness of the release layer to preferably 0.1 μm or more, more preferably 1 μm or more, it is possible to suppress the fusion between the base sheet and the transparent sheet. On the other hand, when the thickness of the release layer is preferably 10 μm or less, more preferably 5 μm or less, the heat transfer property when the transfer material is heat-pressed to the image support can be improved.

  In addition, when matte (matte) processing is performed on the surface of the transparent sheet, the release layer contains various particles, or the surface of the release layer on the side in contact with the transparent sheet is matted. Is preferred. The mat processing is advantageous in that the glossiness of the transparent sheet can be appropriately controlled.

[1-5] Anchor Layer The transfer material may further include an anchor layer 59 like the transfer material 1 in FIG.

  The anchor layer 59 is disposed between the transparent sheet 52 and the color material receiving layer 53. By providing the anchor layer, the adhesive strength between the transparent sheet and the color material receiving layer can be improved, and peeling of the color material receiving layer from the transparent sheet due to a lack of the adhesive strength can be suppressed. The anchor layer improves the adhesiveness between the colorant-receiving layer and the transparent sheet by setting the saponification degree and molecular weight of the water-soluble resin of the colorant-receiving layer to the above-mentioned ranges, and obtains high adhesiveness due to its synergistic effect. Can do. The anchor layer provided between the transparent sheet and the colorant receiving layer needs to release moisture out of the system in the same manner as the transparent sheet. Therefore, it is preferable to perform the treatment for imparting a pore structure to the transparent sheet also on the anchor layer to form pores penetrating the transparent sheet and the anchor layer.

  Further, as the surface modification treatment, the surface of the transparent sheet 52 to be coated with the colorant receiving layer is previously subjected to corona discharge treatment or plasma discharge treatment, or an organic solvent such as IPA or acetone is applied to the transparent sheet 52. Or the surface of the By such treatment of the anchor layer, paintability can be improved and adhesion can be improved. Thus, by forming the anchor layer or performing the surface treatment, the binding property between the colorant receiving layer 53 and the transparent sheet 52 can be increased, the film strength can be increased, and the peeling of the transparent sheet 52 can be prevented.

  Such an anchor layer 59 can be formed using, for example, a thermoplastic synthetic resin, a natural resin, rubber, wax, or the like as a material that enhances the binding property. More specifically, cellulose derivatives such as ethyl cellulose, cellulose acetate propionate, styrene resins such as polystyrene and poly α-methylstyrene, acrylic resins such as polymethyl methacrylate and polyethyl acrylate, polyvinyl chloride, Polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl resins such as polyvinyl butyral, polyvinyl acetal, polyester resin, polyamide resin, epoxy resin, polyurethane resin, ionomer, ethylene acrylic acid copolymer, ethylene-acrylic acid ester Synthetic resins such as copolymers, rosin as tackifier, rosin modified maleic resin, ester gum, polyisobutylene rubber, butyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, polyamide resin, It can be mentioned derivatives of natural resins and synthetic rubber such as Li chlorinated olefins.

  The anchor layer 59 is preferably melted by heat treatment with a heat roller during an adhesion process described later. Due to the melting of the anchor layer 59, the binding property between the color material receiving layer 53 and the transparent sheet 52 can be made stronger without being affected by the unevenness of the surfaces of the color material receiving layer 53 and the transparent sheet 52. . Therefore, the anchor layer 59 is preferably formed of a thermoplastic resin having a glass transition temperature (Tg) of preferably 60 to 160 ° C, more preferably 70 to 140 ° C, and particularly preferably 70 to 100 ° C. On the other hand, when the temperature range is 160 ° C. or higher, the thermoplastic resin is thermally deformed by excessive thermal energy, and thus good adhesion cannot be performed.

[1-6] Hologram Layer The transfer material may further include a hologram layer 58 like the transfer material 1 in FIG. The hologram layer 58 is a layer in which a three-dimensional image is recorded, and is disposed between the transparent sheet 52 and the color material receiving layer 53. The hologram layer provided between the transparent sheet and the colorant receiving layer needs to release moisture out of the system in the same manner as the transparent sheet. Therefore, it is preferable to perform a process for imparting a pore structure to the transparent sheet also on the hologram layer to form pores penetrating the transparent sheet and the hologram layer. By providing the hologram layer, an effect of preventing forgery of recorded matter (credit card or the like) can be obtained. There is no restriction | limiting in particular in the structure of a hologram layer, A conventionally well-known structure is employable. For example, a relief hologram can be mentioned.

  When the anchor layer 59 is provided, the hologram layer 58 can be provided between the anchor layer 59 and the transparent sheet 52 as shown in FIG. The hologram layer 58 is generally composed of a resin layer, and the layer itself may have a single structure or a multilayer structure. The hologram layer may be either a planar hologram or a volume hologram, and is preferably a planar hologram, particularly a relief hologram, from the viewpoints of mass productivity and cost.

  In addition, Fresnel holograms, Fraunhofer holograms, lensless Fourier transform holograms, laser reproduction holograms such as image holograms, and white light reproduction holograms such as rainbow holograms, color holograms using these principles, computer holograms, hologram displays, Multiplex holograms, holographic stereograms, holographic diffraction gratings and the like can be used.

  As a photosensitive material for forming a hologram for recording interference fringes, silver salt, dichromated gelatin, thermoplastics, diazo photosensitive material photoresist, ferroelectric, photochromic material, chalcogen glass, and the like can be used. Moreover, as a material of the hologram forming layer, thermoplastic resins such as polyvinyl chloride, acrylic resin (for example, polymethyl methacrylate), polystyrene, polycarbonate, and unsaturated polyester, melamine, epoxy, polyester (meth) acrylate, urethane Cured thermosetting resins such as (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, triazine acrylate, or the above thermoplastics A mixture of a resin and a thermosetting resin can be used.

  Further, as the material of the hologram layer 58, a thermoformable substance having a radical polymerizable unsaturated group can be used. The hologram layer 58 can be formed by a conventionally known method. For example, when the transparent hologram is a relief hologram, a hologram master on which interference fringes are recorded in an uneven shape is used as a press die. Then, a hologram forming resin sheet is placed on the hologram original plate, and both are heat-pressed by means of a heating roll or the like, and the uneven pattern of the hologram original plate is replicated on the surface of the hologram forming resin sheet. By such a method, a hologram forming layer having a relief forming surface can be obtained.

[1-7] Laminated Structure Basically, the transfer material is formed by sequentially laminating the base material sheet 50, the transparent sheet 52, and the color material receiving layer 53 as in the transfer material 1 of FIGS. It is the laminated structure made. “Substrate sheet, transparent sheet, and color material receiving layer are sequentially laminated” means that the base sheet, transparent sheet, and color material receiving layer are stacked regardless of whether or not another layer is interposed between them. It means that the material sheet, the transparent sheet, and the color material receiving layer are laminated in that order. Therefore, as in the transfer material 1 in FIG. 1C, the structure in which the anchor layer 59 and the hologram layer 58 exist between the transparent sheet 52 and the color material receiving layer 53 is also “base material sheet, transparent sheet, and It is included in the laminated structure in which the color material receiving layers are sequentially laminated.

  The transfer material preferably has a laminated structure in which the base material sheet 50, the transparent sheet 52, and the color material receiving layer 53 are in contact with each other as in the transfer material 1 of FIGS. That is, a structure in which other layers (including sheets) are not interposed between the base sheet 50 and the transparent sheet 52 and between the transparent sheet 52 and the colorant receiving layer 53 is preferable. This is because the thickness of a credit card or the like, which is an object of the recorded material, is strict, and it is desirable to reduce the thickness of the recorded material by reducing the number of stacked layers and sheets.

  As shown in FIG. 1C, when the transfer material 1 includes a release layer 51, an anchor layer 59, and a hologram layer 58, a color material receiving layer 53, an anchor layer 59, a hologram layer 58, a transparent sheet 52, a release sheet 52, It is preferable to have a laminated structure in which the mold layer 51 and the base sheet 50 are sequentially laminated.

[1-8] Shape and Thickness of Transfer Material The transfer material may be in a roll shape or a sheet shape (cut sheet shape) according to the structure of an image recording apparatus or a recorded product manufacturing apparatus described later. In the case of a roll-shaped transfer material, the color material receiving layer may be on the outside or the inside. However, a roll shape in which the color material receiving layer is on the outside and the base sheet is on the inside is preferable so as to optimally correspond to the conveyance mechanism of the image recording apparatus described later.

  The thickness of the base sheet is preferably 1.5 to 5 times the thickness of the colorant receiving layer. By making it 1.5 times or more, curling of a sheet-like (cut sheet-like) transfer material can be prevented, and transferability of the transfer material in an image recording apparatus or recorded product manufacturing apparatus can be improved. it can. On the other hand, by making it 5 times or less, it is possible to improve the heat transfer property when the transfer material is heat-pressed on the image support.

  The transfer material may be a hot peeling type or a cold peeling type. The heat-peelable transfer material is an optimal transfer material for exfoliating the base sheet while the temperature of the laminate of both members is high after the image support and the transfer material are heat-pressed. . On the other hand, the cold-peeling transfer material is an optimal transfer material in which after the image support and the transfer material are heat-bonded, the base sheet is peeled in a state where the temperature of the laminate of these two members is lowered. is there.

  The heat-peeling transfer material is excellent in productivity because the substrate sheet can be peeled immediately after the transfer material is heat-pressed on the image support. For example, productivity can be improved by performing peeling of a base material sheet by a roll-to-roll (roll to roll) using a roll-shaped transfer material. On the other hand, the cold-peeling transfer material can peel the substrate sheet after the temperature of the laminate of both members is lowered after the image support and the transfer material are heat-pressed. For this reason, when a sheet-like (cut sheet-like) transfer material is used, handling when the substrate sheet is peeled after the image support and the transfer material are heat-pressed is facilitated.

[1-9] Manufacturing Method As described above, in the transfer material, the material contained as a component in the constituent material of the transparent sheet constitutes the pores of the open cell structure in the film forming process of the transparent sheet or in the subsequent process ( Foaming (FIG. 36), porous particles (FIG. 37), and hollow particles (FIG. 38)). In addition, pores having an open cell structure can be formed by perforation (FIGS. 39 and 40). A transfer material can be produced by laminating (FIG. 39, FIG. 40) or laminating and bonding such a transparent sheet on a base sheet, and then applying a coating liquid for forming a colorant receiving layer. it can. In addition, after forming a transparent sheet on the substrate sheet, by applying a desired pore treatment to the transparent sheet by another means, and then coating a coating liquid for forming a colorant receiving layer, A transfer material can be manufactured. In addition, after applying a coating liquid for forming a colorant receiving layer to a laminate in which a base sheet and a transparent sheet are sequentially laminated, a desired pore treatment (FIG. 41, FIG. By applying 42), a transfer material can be manufactured. In addition, after applying a coating solution for forming a color material receiving layer to a laminate in which a base sheet and a transparent sheet are sequentially laminated, an image is recorded on the color material receiving layer and then transparent by another means. Desired pore processing (FIGS. 41 and 42) can be applied to the sheet. In the following description, items already described in the transfer material section are omitted, and only items specific to the manufacturing method are described.

[1-9-1] Transparent sheet As the transparent sheet, a sheet that has been surface-modified in advance may be used. By performing surface modification that roughens the surface of the transparent sheet, the wettability of the transparent sheet may be improved, and the adhesion to the colorant receiving layer or the anchor layer may be improved. The method for surface modification is not particularly limited. For example, a method of previously performing corona discharge treatment or plasma discharge treatment on the surface of the transparent sheet; a method of applying an organic solvent such as IPA or acetone on the surface of the transparent sheet; By these surface treatments, the binding property between the color material receiving layer and the transparent sheet is increased, the strength is improved, and the peeling of the material receiving layer from the transparent sheet can be suppressed.

  You may use a transparent sheet in the state made into the laminated body with another layer and a sheet | seat. For example, it is preferable to use a laminated sheet in which an anchor layer, a transparent sheet, a release layer composed of a composition containing a release agent, and a base sheet are sequentially laminated.

  The transparent sheet is formed by using a roll coating method, a rod bar coating method, or a spray coating method with two types of emulsion solution in the transparent sheet and a coating solution containing the foam solution, hollow particles, and porous particles in the emulsion solution. It can be carried out by coating on a substrate by an air knife coating method, a slot die coating method or the like and drying. At this time, it is preferable that the drying temperature after coating is not less than the Tg of the emulsion E1 and less than the Tg of the emulsion E2. By producing a transparent sheet at this temperature, it is possible to produce a transparent sheet in which one of the emulsions is formed and the other remains as particles. At the time of forming the transparent sheet, when it is heated and dried at a temperature of Tg2 or higher, both E1 and E2 are formed into a film, and in the peeling process, cracks are difficult to occur, sufficient edge cutability, peelability from the base sheet. , Stickiness prevention is not obtained. On the other hand, if the transparent sheet is heated at a temperature lower than Tg1, both emulsions E1 and E2 are in a particle state, and it becomes difficult to form a film. Sufficient adhesion to the material receiving layer cannot be obtained. Further, the strength of the transparent sheet is remarkably lowered, and peeling when immersed in a chemical or the like is likely to occur. When the drying temperature at the time of forming the transparent sheet is high, the coating speed can be increased. Therefore, in terms of productivity, the drying temperature at the time of forming the transparent sheet is preferably as high as possible within the above range. In addition, the transparent sheet may be formed by subjecting the material forming the transparent sheet described above to stretching. In addition, it is preferable that a transparent sheet forms a pore by the method described in the formation method of [1-1-2] pore in the process of forming a transparent sheet.

  The release layer can be formed by applying a coating liquid containing a resin or wax constituting the release layer to a resin film or the like constituting the base sheet and drying. Examples of the coating method include conventionally known coating methods such as a gravure recording method, a screen recording method, and a reverse roll coating method using a gravure plate.

[1-9-2] Coating liquid The colorant-receiving layer is prepared by mixing at least a water-soluble resin with an appropriate medium to prepare a coating liquid, applying the coating liquid to the surface of the transparent sheet, and drying it. It is obtained by forming a material receiving layer. When the colorant receiving layer is a void absorption type, at least a water-soluble resin, inorganic fine particles, a water-soluble resin and a cationic resin are mixed with an appropriate medium to prepare a coating solution.

As a medium for the coating liquid, an aqueous medium is preferably used. Examples of the aqueous medium include water; a mixed solvent of water and a water-soluble organic solvent; Examples of water-soluble organic solvents include:
Alcohols such as methanol, ethanol, propanol;
Lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
Ketones such as acetone and methyl ethyl ketone;
And ethers such as tetrahydrofuran;

  Various additives can be contained in the coating liquid as long as the effects of the present invention are not hindered. When a dye ink is used as an ink for recording a reverse image, it is preferable to contain a dye fixing agent. The dye fixing agent can be bonded to the anionic group of the dye molecule to form a salt, thereby making the dye insoluble in water, thereby preventing migration.

  Other additives include, for example, surfactants, pigment dispersants, thickeners, antifoaming agents, ink fixing agents, dot adjusting agents, colorants, fluorescent whitening agents, antioxidants, ultraviolet absorbers, antiseptics Agents, pH adjusters and the like.

  The concentration of the inorganic fine particles in the coating solution may be appropriately determined in consideration of the coating property of the coating solution, and there is no particular limitation. However, it is preferable to set it as 10-30 mass% with respect to the total mass of a coating liquid.

[1-9-3] Coating The colorant receiving layer is formed, for example, by applying a coating liquid on the surface of the transparent sheet constituting the laminate of the base sheet and the transparent sheet. After coating, the coating solution is dried as necessary. Thereby, as shown in FIG. 1B or FIG. 18, the transfer material 1 having a laminated structure in which the base sheet 50, the transparent sheet 52, and the color material receiving layer 53 are sequentially laminated can be obtained.

  In the case of using a laminated sheet in which an anchor layer, a transparent sheet, a release layer, and a base sheet are sequentially laminated, a coating liquid may be applied to the surface of the transparent sheet constituting the laminated sheet. As a result, as shown in FIG. 1C, the transfer material 1 having a laminated structure in which the color material receiving layer 53, the anchor layer 59, the transparent sheet 52, the release layer 51, and the base sheet 50 are sequentially laminated is obtained. be able to.

  As a coating method, a conventionally known coating method can be used. For example, blade coating method, air knife coating method, curtain coating method, slot die coating method, bar coating method, gravure coating method, roll coating method and the like can be mentioned.

The coating amount of the coating liquid is preferably 10 to 40 g / m ^{2 in} terms of solid content. When the coating amount is preferably 10 g / m ² or more, more preferably 15 g / m ² or more, a colorant receiving layer having excellent water absorption in the ink can be formed. Thereby, the ink in the recorded reverse image flows and bleeding of the reverse image can be suppressed. On the other hand, when the coating amount is preferably 40 g / m ² or less, more preferably 20 g / m ² or less, the transfer material is less likely to curl when the coating layer is dried. Further, by reducing the thickness of the color material receiving layer, it is possible to reduce the thickness of the finally formed recorded matter. When the image support is a plastic card such as a credit card, the coating amount is effective because the thickness is strictly defined by the Japanese Industrial Standard (JIS-X-6305). In addition, when providing a drying process at the time of application | coating of the coating liquid for color material receiving layers, it is necessary to make drying temperature less than Tg2 of emulsion E2. When the colorant-receiving layer coating solution is applied by the drying process at the time of forming the transparent sheet, the emulsion E1 forms a film and the emulsion E2 is in a particle state. When the drying temperature at the time of coating the colorant receiving layer becomes Tg2 or more, the emulsion E2 is formed into a film, and both E1 and E2 are formed into a film on the entire transparent sheet, and cracks are not easily generated when the transfer material is transferred. As a result, the edge cutability is reduced.

[1-10] Image FIG. 2A is a perspective view schematically showing a transfer material. An image is recorded on the color material receiving layer of the transfer material. As shown in FIG. 2A, a reverse image 72 is recorded on the color material receiving layer 53 as a mirror image when viewed from the color material receiving layer 53 side and as a normal image when viewed from the transparent sheet 52 side. Is preferred. The reverse image 72 is recorded on the surface of the color material receiving layer 53 on which the transparent sheet 52 is not laminated. The ink jet recording method can improve the productivity of recorded matter and information security and can reduce the recording cost as compared with the conventional thermal transfer method.

  The image recorded on the transfer material may be an image formed with dye ink or an image formed with pigment ink. However, the image is preferably formed with pigment ink. By forming a reversal image with pigment ink, moisture and solvent in the ink hardly remain on the surface of the colorant receiving layer, and drying becomes easy. As a result, poor adhesion between the image support and the transfer material (specifically, the colorant receiving layer) and migration (ink movement) due to moisture or solvent can be effectively suppressed. Furthermore, by forming a reversal image with pigment ink, the light resistance of the reversal image can be improved.

  As shown in FIG. 2B, the pigment component 63 in the pigment ink has a large particle diameter. Therefore, the pigment component 63 does not penetrate into the pores constituted by the inorganic fine particles 65 forming the color material receiving layer 64 in the space absorption type color material receiving layer 64, and the color material receiving layer 64. Fix on the recording surface. Further, unlike the swelling type color material receiving layer, the space absorption type color material receiving layer 64 is kept smooth without swelling the color material receiving layer 64. On the other hand, in the case of a swelling absorption type color material receiving layer, as shown in FIG. 3A, the color material receiving layer 67 is swollen by moisture in the ink, and irregularities are generated on the surface of the color material receiving layer 67. Therefore, the adhesion of the color material receiving layer 67 to the image support is lowered. Further, residual moisture and solvent in the ink may remain on the surface of the color material receiving layer 66, and the adhesion between the image support and the color material receiving layer 66 may be reduced by evaporation of the residual water and solvent in the adhesion process. This is not preferable.

  In the void absorption type color material receiving layer 64, as shown in FIG. 2B, the pigment component 63 in the pigment ink is fixed on the surface of the color material receiving layer 64, while the moisture and solvent in the ink are used. The component 62 penetrates to the inside of the colorant receiving layer 64 and separates (solid-liquid separation) from the pigment component 63. Therefore, since the surface of the color material receiving layer 64 is in a dry state at the time of transfer, adhesion failure due to evaporation of moisture can be suppressed and adhesion can be improved. Further, since the residual moisture and the solvent component 62 remain inside the color material receiving layer 64, the pigment component 63 does not come into contact with the residual moisture and the solvent component 62 again, thereby suppressing ink migration. Can do. On the other hand, in the case of dye ink, as shown in FIG. 3B, the dye component 68 moves (migrate) like the solvent component 69 due to the influence of residual moisture, and bleeding occurs.

  The pigment component in the pigment ink includes a self-dispersing pigment to which at least one functional group of carbonyl group, carboxyl group, hydroxyl group, and sulfone group or a salt thereof is bonded, or a coating around a pigment particle with a resin. Resin dispersion type pigments can be used. Among these, the latter resin-dispersed pigment is preferred because it improves the scratching of the recorded image. Further, by using a resin-dispersed pigment, it is possible to increase the binding force between the pigment particles after being separated from the ink medium, and to form a pigment film on the surface of the colorant receiving layer. In this case, the amount of water on the surface of the pigment film is small. This is because the pigment film substantially blocks water in the lower layer in the colorant receiving layer and further blocks water supply from the lower layer. Therefore, the resin-dispersed pigment component is suitable and suitable for high-speed fixing and high-speed recording of ink. In addition, by incorporating a cationic resin into the color material receiving layer, generally negatively charged pigment particles are electrostatically bonded to the cationic resin, and the adhesion between the color material receiving layer and the pigment ink. To strengthen. Moreover, when using a resin dispersion type pigment as a pigment ink, it is preferable to make the SP value of the dispersion resin and the cationic resin in the colorant receiving layer close to each other. Thereby, the adhesiveness of the resin dispersed pigment to the colorant receiving layer is improved. As such a dispersion resin, it is preferable to use an acrylic resin such as a (meth) acrylic acid ester copolymer.

  In addition, since the dispersion resin is close to the SP value of the water-soluble resin such as polyvinyl alcohol of the colorant receiving layer, when the dispersion resin and the water-soluble resin are melted by heat during transfer, the compatibility between the two increases. The dispersed pigment is firmly adhered to the colorant receiving layer. Therefore, even when the surface of the recorded image is covered with a pigment film, the binding property with the colorant receiving layer can be improved. Furthermore, since the SP value of the dispersion resin is close to the SP value of PVC, PET-G, etc. of the image support, the constituent components of the dispersion resin and the image support surface (PVC, PET-G, etc.) by heat during transfer ) Melts, the compatibility of both increases, and the resin-dispersed pigment is firmly adhered to the image support. Thereby, even if the color material receiving layer surface of the recorded image is covered with the pigment film, the binding property with the image support can be enhanced. Therefore, the transfer performance of the color material receiving layer to the image support can be improved.

  As the resin covering the periphery of the pigment particles, a (meth) acrylic acid ester copolymer having an acid value of 100 to 160 mgKOH / g is preferable. When the acid value is 100 mgKOH / g or more, the ink ejection stability is improved in the ink jet recording system in which the ink is ejected by the thermal system. On the other hand, when the acid value is 160 mgKOH / g or less, the ink particles have a relatively hydrophobic property with respect to the pigment particles, and the fixing property and bleeding resistance of the ink are improved. Therefore, it is suitable for high-speed ink fixing and high-speed recording.

  Here, the acid value is the amount (mg) of KOH required to neutralize 1 g of resin and can serve as an index indicating the hydrophilicity. Moreover, the acid value in this case can also be calculated | required by calculation from the composition ratio of each monomer which comprises a resin dispersing agent. As a specific method for measuring the acid value of the pigment dispersion, Titrino (manufactured by Metrohm) or the like for obtaining an acid value by potentiometric titration can be used.

  The resin used in the pigment dispersion preferably has a dispersing function for satisfactorily dispersing the hydrophobic pigment in the aqueous liquid medium, and a random copolymer is used. Other than the random copolymer, for example, a block copolymer or the like is not preferred because many pigments have high hydrophilicity and many printed images have poor water resistance. The production method of the resin used in the pigment dispersion is a conventional method, and for example, the method disclosed in Japanese Patent No. 4956917 can be used. In addition, about the preferable range of each component and physical property of a pigment ink, what is described in Unexamined-Japanese-Patent No. 2015-110321 can be used, for example.

[1-11] Image Recording As described above, an image is recorded on the surface of the color material receiving layer on which the transparent sheet is not laminated. The image is a reverse image that is a mirror image when viewed from the colorant-receiving layer side and a normal image when viewed from the transparent sheet side. As a result, as shown in FIG. 2A, the reverse image 72 is recorded on the color material receiving layer 53 of the transfer material 1 to form a recording medium (transfer material on which the image is recorded).

  The inkjet recording method is a method of recording an image by ejecting ink (ink droplets) to a transfer material from a plurality of nozzles formed on a recording head. The type of the ink jet recording method is not particularly limited. For example, a thermal ink jet recording method in which ink in a nozzle is foamed by thermal energy generated by a heater in response to a driving pulse and ink droplets are ejected from the nozzle using the foaming energy is preferable.

  Image recording by the ink jet recording method can be performed by an ink jet recording apparatus (ink jet printer). The ink jet printer is preferable in that the image can be recorded extremely stably because the recording head and the transfer material do not contact each other during image recording. The type of ink jet printer is not particularly limited. For example, a full-line type ink jet printer having a line head in which a multi-nozzle head in which a plurality of nozzles including ink discharge ports and ink flow paths are integrated is arranged so as to be orthogonal to the transfer material conveyance direction is used. It is preferable. A full-line type ink jet printer records an image by simultaneously ejecting ink from ink ejection ports of a plurality of nozzles in accordance with conveyance of a transfer material. Therefore, high-quality and high-resolution images can be recorded at high speed.

  The ink discharge amount of the recording head is preferably 20 pl or less. By setting the ink discharge amount to preferably 20 pl or less, more preferably 10 pl or less, and particularly preferably 5 pl or less, the water content of the ink is controlled to an appropriate level in the heat-pressing step between the transfer material and the image support. be able to. Further, as the ejection amount is reduced, the spread of ink in the color material receiving layer can be suppressed, and a dense and sufficiently reversed image can be recorded. Furthermore, the thickness of the image layer (ink layer) can be suppressed.

  Further, as a recording method, a serial head type ink jet recording method may be used in which the relative scanning of the recording head with respect to the recording surface and the transfer of the transfer material on which the image is recorded are repeated. Such a recording method is sufficiently superior to the recording speed of the thermal transfer method, and it is possible to easily record a high-quality image by reducing the droplets.

  The image is preferably recorded on the transfer material with a size larger than that of the image support. Thereby, the recorded image of the transfer material can be transferred to the image support of the recorded material, and as a result, a good image can be recorded on the image support without any margins. If borderless recording is performed directly on the image support by the inkjet method, the ink is absorbed by the edge portion of the image support, and the quality of the image recorded on the edge portion may be degraded. There is. However, as in the present embodiment, an image having a size larger than that of the image support is recorded on the transfer material, and the image is transferred to the image support. Images can be recorded.

[1-11-1] Marking Processing Also, as shown in FIG. 4A, in order to align the transfer material with an automatic laminating machine (transfer section) in a transfer process, which will be described later, when an image is recorded. It is preferable to print 162. As described above, an image is recorded on a transfer material in a range including a recording area 161 corresponding to the size of the image support of the recorded material and an outer area 160, and transferred. Borderless recording can be performed on the image support. An alignment marking 162 is printed outside these areas 160 and 161. By reading this marking 162 with a transmission or reflection type sensor, which will be described later, the bonding position at the time of transfer can be accurately regulated. As shown in FIG. 4B, when the transfer material has a cut sheet shape, a bonding guide 163 is printed on the outside of the recording area 161 in addition to the marking 162, thereby attaching the transfer material at the time of transfer. The alignment position can be easily adjusted.

[1-11-2] Drying of ink In the transfer material on which the image is recorded, the water content of the ink for ink-jet recording forming the image is 70% by mass or less with respect to the total amount of ink to be deposited. It is preferable to dry. By setting the water content of the ink to preferably 70% by mass or less, more preferably 50% by mass or less, rapid evaporation of the ink components can be suppressed when the image support and the transfer material are thermocompression bonded. it can. As a result, it is possible to suppress the decrease in the adhesion strength between the image support and the transfer material and the generation of bubbles remaining in the color material receiving layer. In addition, the amount of water here means the total amount of water, non-volatile solvent, and the like excluding the coloring material.

  The total ink ejection amount can be adjusted by the ink ejection amount of the recording head. In order to easily control the amount of moisture, the amount of ink may be limited in advance by thinning out the number of dots of ink formed during image recording.

  Drying can be performed by a heater (heat source) such as a halogen heater or an exhaust device such as a fan. However, natural drying may be promoted by transporting a sufficiently long transport path without providing a special drying means such as a heater.

[1-12] Pore Treatment As described above, when using a transfer material in which pores are not formed in advance on the transparent sheet, a desired pore treatment means is used for the transfer material after image recording. It is possible to form pores in the sheet. In this case, as shown in FIG. 24, the pores may be formed from the surface side of the colorant receiving layer 53 or from the surface side of the base material sheet 50. In order to maintain good image quality, it is preferable to form pores from the surface of the base sheet 50.

[1-13] Primer Layer In this embodiment, as shown in FIGS. 5 and 66, a primer layer 56 may be further provided on the surface of the color material receiving layer 53 of the transfer material 1 after image recording. As the primer layer, for example, those described in JP-A-2015-110321 can be preferably used.

[2] Recorded Material The recorded material can be configured as shown in FIG. 33 described above, and the color material receiving layer 53 of the transfer material 1 on which the image is recorded is transferred to the image support 55. In the transparent sheet 52 covering the color material receiving layer 53, as described above, the pores 52A are formed, or the open cell structures 553, 554, and 555 are formed. Further, the difference SP2 between the SP value of the image support 55 and the transfer material layer in contact with the image support 55 (in the example of FIG. 1A, the SP value of the color material receiving layer 53 is expressed by the following equation (12). In this case, the compatibility between the image support and the color material receiving layer is increased, and the image support and the color material receiving layer exhibit high adhesiveness: 0 ≦ SP2 ≦ 1.0 (12)

[3] Manufacturing method of recorded matter A recorded matter provided with an image support, a colorant receiving layer, and a transparent sheet is manufactured by a manufacturing method including steps 1, 2, and 3. In step 1, an image is recorded by an inkjet recording method or the like on a color material receiving layer of a transfer material in which a base material sheet, a transparent sheet, and a color material receiving layer containing at least a water-soluble resin are laminated. A transfer material (recording medium) on which an image is recorded is obtained. In step 2, the color material receiving layer of the recording medium is heat-pressed to the image support. In step 3, the substrate sheet is peeled from the recording medium to obtain a recorded matter. In the transparent sheet, pores may be formed in advance as shown in FIGS. 23 and 47 to 49. Further, as described above, pores may be formed in the transparent sheet by a perforating process. In the case of FIG. 24, before the process 2, in the case of FIG. 25, after the process 2, and in the case of FIG. Later, pores are formed by a perforation process.

  Hereinafter, step 2 and step 3 in the method for manufacturing a recorded matter will be specifically described.

  FIG. 6A is a cross-sectional view schematically showing a laminate 84 in which the transfer material 1 is attached to the image support 55. FIGS. 6B and 67 are perspective views schematically showing a recorded matter 73 from which the base sheet 50 has been peeled from the laminate 84 of FIG.

  As shown in FIG. 6A, the color material receiving layer 53 of the transfer material 1 is attached to the image support 55. As a result, a laminate 84 in which the image support 55, the color material receiving layer 53, and the transparent sheet 52 are sequentially laminated is formed, and the reverse image recorded on the color material receiving layer 53 is attached to the image support 55. It is done.

  As shown in FIG. 6B, when the transfer material 1 in which pores are not previously formed in the transparent sheet 52 is used, the surface of the base sheet 50 is formed after the laminate 84 is formed as described above. Fine pores can be formed in the transparent sheet 52 from the side. In that case, as shown in FIG. 25, the pores 50A and 52A can be formed in the base sheet 50 and the transparent sheet 52, and the pores are formed in the base sheet 50, the transparent sheet 52, and the colorant receiving layer 53. 50A, 52A, and 53A can also be formed. As described above, these pores are formed by mechanical drilling such as the needle 657, the spur 650, or the blade shape of FIGS. 46A and 46B, or the laser processing apparatus 658 as shown in FIG. Etc. can be formed. In order to maintain good image recording quality, it is preferable to form the pores 50 </ b> A and 52 </ b> A in the base sheet 50 and the transparent sheet 52.

  As shown in FIGS. 6B and 67, the recorded material 73 is obtained by peeling the base sheet 50 from the laminate 84. As shown in FIG. 6B, when no pores are formed in the transparent sheet 52, the transparent sheet 52 is subjected to perforation as shown in FIG. 52 can be formed with pores 52A.

[3-1] Image support The configuration of the image support is not particularly limited. Examples of the image support include an image support using a resin as a constituent material (resin base support), an image support using paper as a constituent material (paper base support), and the like. Examples of the resin base support include resin cards such as credit cards and IC cards. Examples of the paper base material include a paper booklet such as a passport, a paper card, and the like.

[3-1-1] Resin Base Support The resin constituting the resin base support may be appropriately selected according to the use of the image support, and is not particularly limited. For example,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer;
Polyolefin resins such as polyethylene, polypropylene and polymethylpentene;
Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer;
Aliphatic polyamide resins such as nylon 6 and nylon 6 and 6;
Vinyl polymer resins such as polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, vinylon;
Cellulosic resins such as cellulose triacetate and cellophane;
Acrylic resins such as methyl polymethacrylate, ethyl polymethacrylate, polyethyl acrylate, polybutyl acrylate;
And other synthetic resins such as polystyrene, polycarbonate, polyarylate, and polyimide.

  The resin constituting the resin base support may be, for example, a biodegradable resin such as aliphatic polyester, polycarbonate, polylactic acid, polyvinyl alcohol, cellulose acetate, and polycaprolactone. Moreover, the resin base support body should just be what uses resin as the main structural material, for example, may contain materials other than resin, such as a metal foil.

[3-1-2] Paper base support The type of paper constituting the paper base support is not particularly limited. For example, condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin, polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnation Examples thereof include paper, synthetic rubber latex-impregnated paper, synthetic resin-added paper, paperboard, and cellulose fiber paper.

[3-1-3] Other Resin base support and paper base support may be embossed, signed, IC memory (IC chip), optical memory, magnetic recording layer, anti-counterfeit recording layer (pearl pigment, if necessary) Layer, watermark recording layer, micro characters, etc.), embossed recording layer, IC chip concealing layer, and the like. In addition, the resin base support and the paper base support may be configured as a single layer made of the above-described materials, or may be configured as a multilayer body in which two or more sheets or films having different materials and thicknesses are bonded together. May be.

  Furthermore, the total thickness of the image support is preferably 30 to 800 μm. The thickness of the image support is preferably 30 μm or more, more preferably 500 μm or more, and particularly preferably 650 μm or more. On the other hand, the thickness of the image support is preferably 800 μm or less, more preferably 770 μm or less. When a plastic card is used as the image support, the total thickness of the inkjet recording can be controlled to a total thickness of 0.68 to 0.84 mm described in JIS6301.

[3-2] Laminated Structure The recorded matter 73 has a laminated structure in which the image support 55, the color material receiving layer 53, and the transparent sheet 52 are sequentially laminated as shown in FIGS. Yes. In addition, the transparent sheet 52 in the recorded matter 73 in FIG. 67 has a through-hole 52A.

[3-3] Thermocompression bonding between recording medium and image support As shown in FIG. 6 (a), thermocompression bonding is performed in a state where the image support and the transfer material (recording medium) 1 on which the image is recorded are overlapped. As a result, a laminate 84 is obtained.

  It is preferable to control the temperature of thermocompression bonding to 60-160 degreeC. When the temperature of thermocompression bonding is preferably 60 ° C. or higher, a resin such as a cationic resin or a water-soluble resin in the colorant receiving layer or a thermoplastic resin contained in the primer layer (or anchor layer) is sufficient for adhesion. The image support and the transfer material can be pressure-bonded by being melted to the extent. On the other hand, when the temperature of the thermocompression bonding is preferably 160 ° C. or less, when the image support and the recording medium are thermocompression bonded, the rapid evaporation of the ink component is suppressed, and the image support and the recording medium It is possible to suppress the decrease in the adhesion strength and the generation of bubbles remaining in the colorant receiving layer.

  The emulsion E2 in the recorded matter can be transferred in a sufficiently filmed state by adjusting transfer conditions (for example, transfer temperature and transfer speed), or transferred with some particles remaining. You can also. As shown in FIG. 71, at the time of thermocompression bonding, the transparent sheet portion 980 of the portion 963 where the image support 55 and the color material receiving layer are bonded and the transparent portion 964 where the image support and the color material receiving layer are not bonded are transparent. The sheet portion 981 can be controlled to have a different film state. That is, at the time of thermocompression bonding, since the heat of the heat roll is easily transmitted to the transparent sheet portion 980, a state in which a part of the emulsion E2 is formed into a film and some particles remain (FIG. 71 (b)), or an emulsion of the transparent sheet E2 is completely filmed (FIG. 71 (c)). At this time, the emulsion E2 that is partially or completely formed into a film can strengthen the bonding strength with the emulsion E1 that has been formed into a film in advance, thereby enhancing the film strength of the transparent sheet. On the other hand, since the heat of the heat roll is not transmitted to the transparent sheet portion 981, the emulsion E2 can be left in a particle state. Since the film state is different between the transparent sheet portion 980 and the transparent sheet portion 981, in the peeling process, cracks are easily generated with the boundary portion 982 as a base point. From the above, the foil breakage can be improved by using two types of emulsions and changing the film state of the emulsion E2 using the temperature at the time of thermocompression bonding. Depending on the performance required by the user, the state in which some particles of the emulsion E2 are formed into a film and the state in which the emulsion E2 is completely formed into a film can be properly used.

  The method for thermocompression bonding is not particularly limited. For example, a method of laminating a recording medium on an image support to form a laminated body, and sandwiching the laminated body between a pair of heat rollers can be used. In that case, the surface temperature of the heat roller is preferably 100 to 180 ° C. Thereby, even when the conveyance speed of a laminated body is quick and heating time cannot fully be taken, a laminated body can be heated at 60-160 degreeC.

  When using the manufacturing apparatus 25 described later as shown in FIGS. 9 and 28 to 31, it is preferable to use a silicone roller as the heat roller 22 in contact with the image support 55 side. Since the SP value of the silicone roller is around 8.7, when the image support 55 is not present between the heat rotors 21 and 22, that is, when the color material receiving layer 53 is in contact with the heat roller 22, As a result, the colorant receiving layer 53 becomes difficult to adhere. Therefore, transfer of the color material receiving layer 53 to the heat roller 22 can be prevented. The heat roller 21 heats the recording medium from the base material sheet 50 side.

[3-4] Peeling of base material sheet and release layer By peeling the base material sheet 50 from the laminate 84 of FIG. 6A, an ink jet recorded product 73 is obtained. In the recorded matter 73, the transparent sheet 52 positioned at the uppermost layer protects the reverse image 72 recorded on the color material receiving layer 53 on the lower layer side. When the primer layer is provided, the image support 55 is sufficiently closely fixed to the color material receiving layer 53 through the primer layer.

  In the case where the transfer material is peeled off when heated, it is preferable that the substrate sheet is peeled immediately after the thermocompression bonding and before the temperature is lowered. In the case of a hot peeling type, it is preferable to peel the base sheet using a peeling mechanism having a separation claw 86 as shown in FIG. 7A or a peeling roll 88 as shown in FIG. 7B. . In such a peeling method, when the transfer material is supplied by roll-to-roll, that is, the roll-shaped transfer material is fed out and supplied, and the base material sheet of the transfer material is wound into a roll shape. In this case, it is effective in increasing productivity.

  When the transfer material is a cold release type, the substrate sheet can be released even when the temperature is lowered. Therefore, since not only peeling by a roll or a peel mechanism but also manual peeling is possible, it is particularly suitable when the base sheet is processed into a cut sheet. In the case where the transfer material is supplied by roll to roll, the peeling angle θ is 0 to 165 °, more preferably 90 ° to 165 °. By setting the peeling angle θ, it is possible to prevent the patch portion separated by the pre-cut processing of the transfer material described later from being inadvertently peeled off or turned up. The conveyance angle θ in FIG. 7B is not limited to the above angle.

  In the thermocompression bonding and peeling step, a known two-roll type or four-roll type laminating machine may be used. The 4-roll type is preferably used because the heat at the time of thermocompression bonding can be easily transmitted and the peeling process can be easily performed as compared with the 2-roll type.

[3-5] Double-sided simultaneous peeling When transferring the transfer material on which the image is recorded on both sides of the image support simultaneously, the images on the upper transfer material 92 and the lower transfer material 94 are transferred as shown in FIG. It is preferable to shift the recording position. As a result, when the swelling type color material receiving layer is used in the heat roller transfer, the SP value is the same, so the color material receiving layers may adhere to each other. Is possible. Further, the base material sheet can be easily peeled off by the peel part 90.

[3-6] Formation of pores in transparent sheet As described above, when the transfer material 1 in which pores are not previously formed in the transparent sheet 52 is used, the base material sheet 50 is formed after the laminate 84 is formed. It is possible to form pores in the transparent sheet 52 from the front surface side. That is, as shown in FIG. 25, the pores 50A and 52A can be formed in the base sheet 50 and the transparent sheet 52, and the pores 50A and 52A are formed in the base sheet 50, the transparent sheet 52, and the colorant receiving layer 53. , 53A can also be formed. As described above, these pores are formed by mechanical drilling such as the needle 657, the spur 650, or the blade shape of FIGS. 46A and 46B, or the laser processing apparatus 658 as shown in FIG. 46C. Etc. can be formed. In order to maintain good image recording quality, it is preferable to form the pores 50 </ b> A and 52 </ b> A in the base sheet 50 and the transparent sheet 52.

[4] Inkjet recording apparatus The recording apparatus in FIG. 27 records an image by applying a coloring material to a supply unit that feeds a transfer material to a conveyance path and a coloring material receiving layer of the transfer material that is fed to the conveyance path. And a recording unit 6. In addition, when using the transfer material in which pores are not formed in the transparent sheet, as described above, after the step 2 (FIG. 24), after the step 2 (FIG. 25), or after the step 3 In the step (FIG. 26), a perforation processing part 659 for forming pores in the transparent sheet is provided. 27 is provided so as to form pores in the transparent sheet in the previous step of step 1.

[4-1] Inkjet recording apparatus Specifically, the recording apparatus includes an inkjet recording apparatus that records an image by ejecting ink (ink droplets) onto a transfer material from a plurality of nozzles formed on a recording head. Inkjet printers can be used. Such a recording apparatus is preferable because an image can be recorded extremely stably because the recording head and the transfer material do not come into contact with each other during image recording. The inkjet recording method is not particularly limited, and both the thermal method and the piezo method can be suitably used. The thermal ink jet recording method, in which the ink in the nozzle is foamed by the heat energy of the heater that generates heat in response to the drive pulse and ink droplets are ejected from the nozzle using the foaming energy, is higher than other recording methods. The resolution is preferable. In addition, a full-line type ink jet printer having a line head in which a multi-nozzle head in which a plurality of nozzles including ink discharge ports and ink flow paths are integrated is arranged so as to be orthogonal to the transfer material conveyance direction is used. It is preferable. This full-line type ink jet printer records an image by simultaneously ejecting ink from the ink ejection ports of a plurality of nozzles in accordance with the transfer of the transfer material. Therefore, high-quality and high-resolution images can be recorded at high speed.

[4-2] Formation of pores in transparent sheet As described above, when the transfer material 1 in FIG. 1B in which the pore structure is not previously formed is used in the transparent sheet, the recording apparatus in FIG. Fine pores can be formed in the transparent sheet by mechanical drilling or laser processing.

[5] Recorded Product Manufacturing Apparatus The recorded product manufacturing apparatus includes a recording apparatus as shown in FIG. 27, an image support supply unit that sends the image support to the transport path, and a transfer to the image support sent to the transport path. An attachment portion for attaching the material and a peeling portion for peeling the base sheet from the transfer material are provided. In the case of using a transfer material in which the pore structure is not previously configured for the transparent sheet, a punching processing unit 659 corresponding to the punching process as shown in FIGS. 24 to 26 is provided.

[5-1] First Manufacturing Apparatus FIG. 9 shows a first configuration example of a manufacturing apparatus 25 (hereinafter referred to as “first”) for manufacturing a recorded matter using a transfer material in which pores are previously formed in a transparent sheet. 1 is a side view schematically showing a manufacturing apparatus 1).

[5-1-1] Main Configuration The manufacturing apparatus 25 includes a supply unit 4 and a recording unit 6. The supply unit 4 sends the transfer material 1 in which pores are formed in advance in a transparent sheet and wound in a roll shape, to the conveyance path. The recording unit 6 directly discharges water-based ink containing a color material, water, a non-volatile organic solvent, and the like onto the transfer material 1 sent to the conveyance path, and records a reversed image.

  Further, the manufacturing apparatus 25 evaporates moisture in the transfer material 1 to which ink has been applied, and the drying unit 7 for improving the adhesion to the image support 55 and the evaporated moisture in the apparatus. And a fan 10 for preventing condensation. Further, the manufacturing apparatus 25 includes the preheating unit 19 for heating the image support 55 to improve the adhesion to the transfer material 1, the color material receiving layer on which the reverse image is recorded, and the transparent sheet. And an attaching portion 29 to be attached to 55. Furthermore, a curl correction unit 150 that corrects the curl of the image support 55 after being attached, a peeling unit 151 that peels the base sheet, an image reversing unit 152 that reverses the image support 55 when performing double-sided recording, and an image A discharge unit 26 for discharging and accumulating the recorded image support 55 is provided.

[5-1-2] Operation The supply unit 4 rotates the roll-shaped transfer material 1 wound so that the color material receiving layer is positioned on the outside in the direction indicated by the arrow in the drawing, thereby transferring the transfer material. 1 is sent to the recording unit 6. The transfer material 1 is guided by a guide plate (not shown), is sandwiched between the grip roller 3 and the nip roller 2, and is transported to the recording unit 6 in a flat state.

  When conveyance of the transfer material 1 is started from the supply unit 4, the sensor unit 31 detects the marking, and the recording unit 6 records a reverse image on the color material receiving layer of the transfer material 1. Thereafter, the transfer material 1 passes through the drying unit 7. The drying unit 7 evaporates water or the like in the ink that forms the reverse image, and the fan 10 exhausts the evaporated water. Thereby, the transfer material 1 in which the reverse image is recorded on the color material receiving layer is obtained. At this time, the above-described marking printing is also performed.

  On the other hand, the supply unit 12 supplies the image supports 55 one by one to the attachment part. The resist guide 14 aligns the image support 55 and the transfer material 1, and the transfer material 1 is laminated on the image support 55. The laminated body of the image support 55 and the transfer material 1 is conveyed to the attaching portion 29. The adhering portion 29 includes a pair of heat rollers 21 and 22, and the image support 55 and the transfer material 1 are heat-pressed when the laminate passes between the rollers.

  Thereafter, the laminate of the image support 55 and the transfer material 1 is conveyed to the curl correction unit 150 to correct the curl, and then the base material sheet and the release layer of the transfer material 1 are peeled off at the peeling unit 151. Then, it is wound on the winding roll 24. When performing double-sided recording, the image inverting unit 152 inverts the image support 55 and back-feeds it to the registration guide 14. Then, in the recording unit 6, the reverse image to be transferred to the back surface of the image support 55 is recorded on the color material receiving layer of the transfer material 1 and back-fed to the resist guide 14 in the same manner as when recording on the front surface. The reverse image is transferred to the back surface of. In this way, a recorded matter in which the transfer material 1 is heat-pressed to the image support 55 can be obtained.

[5-1-3] Connection between First Manufacturing Apparatus and Controller The manufacturing apparatus 25 is connected to the controller 41 via the network 47 as shown in FIG. The manufacturing apparatus 25 can also be connected to the controller 41 via a serial port, a parallel port, a USB port, or the like without using the network 47. The CPU provided in the control unit 44 of the manufacturing apparatus 25 is connected to the recording unit, the drying unit, the adhering unit, the curl correcting unit, the peeling unit, and the image inverting unit, and controls their operations.

  The network 47 is a network such as the Internet or a local area network (LAN), and may be wired or wireless. The controller 41 is a computer for controlling the manufacturing apparatus 25. In the controller 41, the control unit 44, the display unit 45, the input / output unit 46, the storage unit 42, and the communication unit 43 are connected to each other via a system bus 48. The controller 41 may be connected to a digital camera, a drive device for reading image data, and a plate making device.

  The control unit 44 includes a CPU, a RAM, a ROM, and the like. The CPU calls and executes a program stored in the ROM or the like in a work memory area on the RAM, performs arithmetic processing and operation control, and controls the entire system. The ROM is a non-volatile memory and permanently stores programs, data, and the like. The RAM is a volatile memory, and temporarily stores programs, data, and the like.

  The display unit 45 is a display device such as a CRT monitor or a liquid crystal panel, and includes a logic circuit or the like (video adapter or the like) for realizing a video function of a computer in cooperation with the display device. The input / output unit 46 is a part that inputs and outputs data. Examples of data input include a keyboard, a pointing device such as a mouse, a numeric keypad, and the like. Through these input units, operation instructions, operation instructions, data input, maintenance management, etc. It can be performed. Further, by connecting a scanner, a drive device (not shown) or the like to the input / output unit 46, input data from these external devices can be transferred to the control unit 44, and data can be output to the external device. .

  The storage unit 42 is a device that stores data, and a magnetic disk, a memory, an optical disk device, or the like can be used. The storage unit 42 stores a program executed by the control unit 44, data necessary for program execution, an OS (Operating System), and the like. Moreover, the pattern recorded by the recording part 6 of the manufacturing apparatus 25 can also be stored. The communication unit 43 is a communication interface that mediates communication between the controller 41 and the network 47, and includes a communication control device, a communication port, and the like. A personal computer or the like can be used instead of the controller 41.

[5-1-4] Control System FIG. 11 is a block diagram showing a configuration of a control system provided in the recording unit 6 of FIG. Recording data and commands transmitted from the host PC 120 are received by the CPU 100 via the interface controller 102. The CPU 100 is an arithmetic processing unit that performs overall control such as reception of recording data of the recording unit 6, recording operation, and handling of the transfer material 1. After analyzing the received command, the CPU 100 develops the image data of each color component of the recording data in the image memory 106 as a bitmap. Before the image recording, the capping motor 122 and the head up / down motor 118 are driven via the output port 114 and the motor driving unit 116, and the recording head 22 (22K, 22C, 22M, 22Y) is moved from the capping position (standby position). Move to the recording position (image forming position). The recording heads 22K, 22C, 22M, and 22Y are recording heads that eject black (Bk), cyan (C), magenta (M), and yellow (Y) inks, respectively. Thereafter, the position of the transfer material is detected by the sensor unit 31 (tip detection sensor) in order to determine the timing (recording timing) at which ink starts to be ejected from the transfer material conveyed at a constant speed. Thereafter, in synchronism with the transfer of the transfer material, the CPU 100 sequentially reads out the recording data corresponding to each ink color from the image memory 106, and the recording data is transferred to the corresponding recording head 22 </ b> K via the recording head control circuit 112. Transfer to 22C, 22M, 22Y. As a result, the ejection energy generating elements (such as heaters and piezo elements) provided in each nozzle of the recording head are driven based on the recording data, and ink droplets are ejected from the nozzles corresponding to the driven ejection energy generating elements. . The ejected ink droplets land on the color material receiving layer (ink receiving portion) of the transfer material at the position facing the recording head to form dots. A desired image is recorded by the set of dots.

  Such an operation of the CPU 100 is executed based on a processing program stored in the program ROM 104. The program ROM 104 stores a processing program corresponding to the control flow, a table, and the like. A work RAM 108 is used as a working memory.

[5-1-5] Operation Flow of First Manufacturing Apparatus Next, the operation flow of the manufacturing apparatus (first manufacturing apparatus) 25 of FIG. 9 will be described according to the flowchart of FIG. The processing according to this operation flow is executed by the CPU 100 of the recording unit in FIG.

  The CPU of the recording unit determines whether or not the recording data is transmitted from the controller via the network or various ports (step S101), and when the recording data is transmitted, the image from the supply unit is not transferred. The material supply is started (step S102). If the marking is not detected by the sensor unit, that is, if the sensor unit is OFF, the recording unit starts a recording operation on the transfer material (steps S103 and S104). After the recording operation is completed (step S105), excess moisture is evaporated from the transfer material on which the image is recorded by the drying process of the drying unit (step S106). Thereafter, the image support and the transfer material are aligned in the resist guide (step S107). After completion of the alignment, the transfer material and the image support are bonded at the attachment portion (steps S108 and S109). The above operations are all based on the time point when the sensor unit detects the marking.

  On the other hand, when the CPU determines that the recording data has been transmitted, the image support is fed from the supply portion of the image support to the attachment portion (steps S107 and S108). In the resist guide, the image support and the transfer material are aligned (step S111). After completion of the alignment, the transfer material and the image support are bonded at the attachment portion (steps S112 and S113). Thereafter, the substrate sheet of the transfer material is peeled off as it is conveyed to the peeling portion, and the recorded matter (final recorded matter) is discharged and stacked on the discharge portion (step S114).

[5-1-6] Process Executed by First Manufacturing Apparatus [5-1-6-1] Position Detection of Transfer Material The sensor unit 31 in FIG. 9 performs transfer in order to synchronize the operation of the adhesion portion. The position of the material 1 is detected, and the CPU controls each part based on the detection result. A reflective or transmissive optical sensor is used to detect the marking.

[5-1-6-2] Pre-cut treatment If necessary, after forming the color material receiving layer on the transfer material, cut the color material receiving layer and a part of the transparent sheet from the color material receiving layer side. You may perform a precut process. In the precut process, after the transfer material on which the reverse image is recorded and the image support are bonded, the transparent sheet can be cut cleanly from the notch. Thereby, a strong protective layer can be formed with a transparent sheet having a uniform thickness, and sufficient durability can be imparted to the reverse image formed on the colorant receiving layer. As a preferable precut treatment, a treatment method is disclosed in JP-A No. 2015-110321.

[5-1-6-3] Recording Process As described above, according to the ink jet recording apparatus, the recording head and the transfer material are not in contact with each other, so that an image can be stably recorded. In the case of the line type, a high-resolution and high-quality image can be recorded at high speed.

  In the manufacturing apparatus 25 of FIG. 9, the transfer material 1 passes through a guide plate (not shown) and enters the recording unit 6 while being sandwiched between the grip roller 3 and the nip roller 2. The recording unit 6 records an image on the color material receiving layer of the transfer material 1 by ejecting ink from the recording head 6 according to the image data.

[5-1-6-4] Water Evaporation Control If the ink remains on the surface of the color material receiving layer containing ink during image transfer, poor adhesion between the color material receiving layer and the image support occurs. There is a fear. Due to the heating during the transfer, the ink component and ink remaining on the surface of the color material receiving layer may be rapidly evaporated, resulting in poor adhesion and partial remaining of bubbles in the color material receiving layer. Therefore, it is preferable to dry the transfer material in the transfer material conveyance path from when the image is recorded to when the image is transferred. In that case, natural drying may be promoted by sufficiently lengthening the conveyance path of the transfer material before transfer without providing a special drying means such as a heater. Further, in consideration of the evaporated ink component, air flow control and exhaust means inside the recording apparatus may be required. In the manufacturing apparatus 25 of FIG. 9, when the transfer material 1 on which an ink image is recorded passes between the drying unit 7 and a guide plate (not shown), a heat source such as a halogen, a blower, or a drying unit 7 combining them. As a result, water, which is the main component of the ink, and some volatile solvent components are evaporated. Further, the air flow and exhaust are controlled by the fan 10 in order to prevent condensation of the evaporated gas in the recording apparatus. By using the control of the airflow in combination, it is possible to improve the saturated vapor pressure on the surface of the colorant receiving layer and promote drying.

  By such ink moisture control, the amount of ink moisture (total amount of water, non-volatile solvent, etc. excluding the color material) in the coloring material receiving layer during the adhesion process in the adhesion portion 29 is compared to the total ink deposition amount. , Preferably 70% or less, more preferably 50% or less. When the water content of the ink remains 70% or more, although depending on the thickness of the color material receiving layer, the ink component remaining on the surface of the color material receiving layer or the rapid evaporation of the ink causes poor adhesion or the color material receiving layer. There is a possibility that partial bubble remaining or the like may occur. Although the total ink ejection amount varies depending on the ejection amount of the recording head, it is set in advance to an appropriate amount by thinning out the number of dots during image recording so that the moisture control as described above is appropriately performed. can do.

[5-1-6-5] Adhering Step As shown in FIG. 9, the transfer material 1 on which an image is recorded is guided by a guide plate (not shown) and moves to the attaching portion 29 including the heat rollers 21 and 22. The sheet-like sheet-shaped image support 55 is stacked on the supply unit 12, the position of which is corrected by the registration guide 14, and then supplied to the attachment unit 29 in accordance with the transfer of the transfer material 1. The supply unit 12 is supplied from the lower side in order to prevent dust from adhering to the image transfer surface of the image support 55 and contamination from the rubber roll during pickup.

  The transfer material 1 and the image support 55 are stacked and conveyed between the heat rollers 21 and 22 so that the color material receiving layer of the transfer material 1 on which the image is recorded and the image support 55 are in contact with each other. By heating, the image support 55 and the transfer material 1 are bonded. Thereafter, the base material sheet of the transfer material 1 is peeled off. As a result, the image support 55 is in a state in which the transparent sheet is attached together with the color material receiving layer on which the image is recorded. That is, on the image support 55, the transparent sheet is positioned in the uppermost layer as a protective film, and the image is positioned under the protective film.

  Heating to the transfer material at the time of thermocompression bonding is performed mainly by heat transfer from the side of the base material sheet of the transfer material, not from the side of the thick image support such as a plastic card. In the adhesion process by the adhesion part 29, the maximum temperature reached by the color material receiving layer is controlled so that the water-soluble resin component of the color material receiving layer is not less than the glass transition temperature and does not exceed the evaporation temperature of water, which is the main component of the ink. do it. That is, the surface temperature of the heat roller when the transfer material 1 and the image support 55 are bonded is such that the water-soluble resin of the color material receiving layer is sufficiently melted and the water is evaporated to transfer the transfer material 1 and the image support. The temperature may be any temperature that does not cause bubbles to be generated between the temperature and 55. In addition, when the conveyance speed is high and the heating time by the heat source cannot be secured sufficiently, there is a possibility that a temperature difference occurs between the heat source and the color material receiving layer. In this case, the surface temperature of the heat roller may be controlled to be higher than usual, such as 100 to 180 ° C. In addition, when heated in a closed space, the boiling point rises due to an increase in pressure, and the water evaporation temperature rises in the colorant receiving layer sandwiched between the primer layer and the transparent sheet layer. The temperature may be controlled to be higher in consideration of the foil breakability of the part.

[5-1-6-6] Preheating If necessary, the preheating unit is provided between the supply unit 12 and the adhering unit in order to improve the adhesion to the transfer material 1 by heating the image support 55. May be provided. By the preheating, the surface of the image support (card etc.) 55 before the transfer material 1 is attached can be appropriately heated.

[5-1-6-7] Curling Correction As shown in FIG. 9, after the image support 55 and the transfer material 1 are attached, the curling of the image support 55 is corrected by the curl correction unit 150. Make it flat. While the image support 55 is warm, the curl of the image support 55 can be corrected by sandwiching it between the heating plate and the support plate in the curl correction unit 150.

[5-1-6-8] Peeling Process As shown in FIG. 9, the base material sheet 50 in the transfer material 1 that has passed through the adhering portion 29 is peeled off at portions other than the image recording area, and is taken up by the take-up roll 24. It is wound up. Further, the image support 55 to which the image is transferred is conveyed to the discharge unit 26 and accumulated one by one.

[5-1-6-9] Image Inversion Device When images are transferred to both sides of the image support 55, it is preferable that the manufacturing apparatus 25 includes an image inversion unit 152 as shown in FIG. The image support 55 (recorded material) after the image is transferred to one surface (front surface) of the image support 55 and the base sheet 50 is peeled from the surface is inverted by the reversing device 152. . The recorded matter is fed back to the resist guide 14 in order to transfer the image to the other side (back side). At the same time, the transfer material 1 is also fed back, and after that feedback, the image is transferred to the back side of the recorded material by performing the same processing as the front side image recording in the recording unit, the adhesion unit, the curl correction unit, and the peeling unit. The

  As shown in FIG. 13, the manufacturing apparatus 25 may include a transfer unit 13 for transferring a primer to the transfer material 1 after recording an inkjet image on the transfer path of the transfer material 1. The primer is for adhering the image support 55 aligned in the resist guide 14 to the transfer material 1.

  The transfer material 1 is supplied to the transfer unit 13 one by one. In the transfer unit 13, the primer sheet is supplied from a supply roll 15 (primer supply roll), passes between the thermal head 30 and the transfer material 1, and passes through a guide roll 16 to a winding roll 17 (primer winding roll). It is wound up. The primer is transferred to the transfer material 1 by the thermal head 30. The thermal head 30 generates heat by applying energy corresponding to the heat capacity that varies depending on the thickness and material of the primer, and the primer is transferred to the transfer material 1 to form an adhesive layer. When the thermal head 30 partially heats the primer sheet (selective heating), it is possible to perform selective primer transfer that does not transfer the primer to special parts that do not require surface coating, such as IC parts. Become. When a primer layer is applied to the entire surface of the transfer material 1, primer transfer can be performed using an inexpensive heating means such as a heat roller.

[5-2] Second Manufacturing Apparatus FIG. 28 is an explanatory diagram of a second configuration example (hereinafter, also referred to as “second manufacturing apparatus”) of a recorded matter manufacturing apparatus. The second manufacturing apparatus 25 uses the transfer material 1 in which the pore structure is not previously configured in the transparent sheet. This 2nd manufacturing apparatus is the structure provided with the punching process part 659 for providing a pore to a transparent sheet with respect to the 1st manufacturing apparatus mentioned above. This perforation processing part 659 gives pores to the transparent sheet of the transfer material 1 before image recording. A description of the same parts as those of the first manufacturing apparatus is omitted.

  The perforating part 659 can form pores in the transparent sheet from either the colorant receiving layer side or the base sheet side of the transfer material. In order to maintain the quality of the recorded image, it is preferable to perforate from the base sheet side as shown in FIG. Moreover, such a perforation process should just form a pore at least in a transparent sheet like FIG. The drilling is performed by mechanical drilling such as a needle 657, a spur 650, and a blade shape as shown in FIGS. 46 (a) and 46 (b), or laser processing by a laser processing device 658 as shown in FIG. 46 (c). There may be.

[5-3] Third Manufacturing Apparatus FIG. 29 is an explanatory diagram of a third configuration example (hereinafter, also referred to as “third manufacturing apparatus”) of a recorded matter manufacturing apparatus. The 3rd manufacturing apparatus 25 uses the transfer material 1 by which the pore structure is not previously comprised by the transparent sheet. This third manufacturing apparatus is different from the second manufacturing apparatus in the position where the drilling unit 659 is provided. That is, the perforation processing unit 659 in the third manufacturing apparatus is arranged so as to give pores to the transparent sheet of the transfer material 1 after image recording. A description of the same parts as those of the second manufacturing apparatus is omitted.

[5-4] Fourth Manufacturing Apparatus FIG. 30 is an explanatory diagram of a fourth configuration example (hereinafter also referred to as “fourth manufacturing apparatus”) of a recorded matter manufacturing apparatus. The 4th manufacturing apparatus 25 uses the transfer material 1 by which the pore structure is not previously comprised by the transparent sheet. This fourth manufacturing apparatus is different from the second and third manufacturing apparatuses in the position where the drilling unit 659 is disposed. That is, as shown in FIG. 25, the punching unit 659 in the fourth manufacturing apparatus gives pores to the transparent sheet of the transfer material 1 after the image is transferred and before the substrate sheet is peeled off. Have been deployed. A description of the same parts as those of the second manufacturing apparatus is omitted.

[5-5] Fifth Manufacturing Apparatus FIG. 31 is an explanatory diagram of a fifth configuration example (hereinafter also referred to as “fifth manufacturing apparatus”) of a recorded matter manufacturing apparatus. The fifth manufacturing apparatus 25 uses the transfer material 1 in which the pore structure is not previously configured in the transparent sheet. This fifth manufacturing apparatus is different from the second, third, and fourth manufacturing apparatuses in the position where the drilling unit 659 is disposed. That is, as shown in FIG. 26, the punching unit 659 in the fifth manufacturing apparatus gives pores to the transparent sheet of the transfer material 1 after the image is transferred and the base material sheet is peeled off. Have been deployed. A description of the same parts as those of the second manufacturing apparatus is omitted.

[5-6] Sixth Manufacturing Apparatus In the sixth configuration example (hereinafter also referred to as “sixth manufacturing apparatus”) of the recorded product manufacturing apparatus, the printer unit and the transfer unit are configured separately and independently. ing.

  14A is a perspective view of the printer 301 that records an image on the transfer material 1, and FIGS. 14B and 15A are explanatory views of a conveyance mechanism 302 that conveys the transfer material 1. FIG. . First, the roll-shaped transfer material 1 in which the color material receiving layer 53 is wound outward as shown in FIG. 15B is set on the unwinding roll 313 in FIG. The transfer material 1 is transported to a recording position facing the recording head 311 by the transport belt 310 and a reverse image is recorded, and then is wound as a recording medium by a winding roll 314.

  Next, a roll-shaped transfer material (recording medium) 1 on which an image has been recorded is set on the unwinding roll 201 of the laminating machine shown in FIG. The image support 55 is supplied from the supply unit 206, and the transfer material 1 is conveyed from the unwinding roll 201 to the transfer unit 203. Marking of the transfer material is detected by the sensor 208 and is aligned with the image support 55, and then the transfer material is heat-pressed with the image support 55 by the transfer roll 204. Then, after the base material sheet 50 of the transfer material 1 is peeled off by the peeling roll 207, it is wound up by the winding roll 202. As shown in FIG. 17A, when the roll-shaped (inner winding roll) transfer material 1 wound with the base sheet 50 outside and the color material receiving layer 53 inside is used, FIG. The conveyance path configured as shown in (b) is used. In such an inner roll form, dust can be prevented from adhering to the surface of the colorant receiving layer.

  When a transfer material having a pore structure not previously formed is used for the transparent sheet, as shown in FIGS. 50A and 50B, before and after the image recording process by the recording head 311, the punching processing unit 659 makes the transparent sheet transparent. It is possible to form pores in the sheet. Alternatively, as shown in FIGS. 51 (a), 51 (b), and 51 (c), before the transfer process by the laminator, after the peeling process of the base material sheet, and before the peeling process of the base material sheet, the perforation processing unit 659 You may form a pore in a transparent sheet. Further, the punching unit 659 may constitute a punching device that is independent from the printer unit and the transfer unit. In this case, in order to form the pores in the state of the transfer material, it is preferable to provide an independent punching portion as shown in FIG. 56 (a) between the printer portion and the transfer portion. Further, in order to form pores after the substrate sheet is peeled off, it is preferable to provide an independent perforating part for perforating after the image transfer step as shown in FIG.

[5-7] Seventh Manufacturing Apparatus In a seventh configuration example (hereinafter also referred to as “seventh manufacturing apparatus”) of a recorded product manufacturing apparatus, a printer unit and a transfer unit are configured separately and independently. ing. As shown in FIG. 18, the manufacturing apparatus is configured such that after an image is recorded on the transfer material 1, the transfer material 1 is cut into a sheet shape by a cutting mechanism 315 and then discharged to a discharge unit 316. . Thereafter, the cut transfer material 1 is manually aligned with the image support 55 as shown in FIG. 19, and then heat-pressed by the transfer roll 204 constituting the transfer unit 203 and then discharged to the discharge unit 205. Is done. Thereafter, the substrate sheet is manually peeled off to obtain a recorded matter. Further, by simultaneously recording the bonding guide when recording an image on the transfer material, it is possible to manually align them while visually confirming that the image support 55 is along the bonding guide.

  When using a transfer material in which the pore structure is not previously configured for the transparent sheet, the punching section 659 is used before and after the cutting process of the transfer material 1 by the cutting mechanism 315 as shown in FIGS. 52 (a) and 52 (b). Thus, pores can be formed in the transparent sheet. Alternatively, as shown in FIGS. 53 (a) and 53 (b), before and after the transfer process by the laminating machine, pores may be formed in the transparent sheet by the perforating part 659. Further, the punching unit 659 may constitute a punching device that is independent from the printer unit and the transfer unit. In this case, in order to form the pores in the state of the transfer material, it is preferable to provide an independent punching portion as shown in FIG. 57 between the printer portion and the transfer portion. In order to form the pores after the substrate sheet is peeled off, it is preferable to provide an independent perforation processing part for perforating after the image transfer step as shown in FIG.

[5-8] Eighth Manufacturing Apparatus In an eighth configuration example (hereinafter also referred to as “eighth manufacturing apparatus”) of a recorded product manufacturing apparatus, a printer unit and a transfer unit are configured separately and independently. ing.

  20A is a perspective view of the printer 401 that records an image on the transfer material 1 processed into a cut sheet shape, and FIG. 20B is a schematic configuration diagram of the transport mechanism 402 in the printer 401. The transfer material 1 set in the supply unit of the printer 401 is conveyed to a recording position facing the recording head 311 by the conveyance belt 310, and after a reverse image is recorded, it is discharged as a recording medium to the discharge unit 414. Thereafter, the transfer material 1 on which the image has been recorded and the image support 55 are heat-pressed by the laminating machine shown in FIG. 19, and then the base material sheet is manually peeled off to obtain a recorded matter. Further, by simultaneously recording the bonding guide when recording an image on the transfer material, it is possible to manually align them while visually confirming that the image support 55 is along the bonding guide.

  When a transfer material that does not have a pore structure formed in advance is used for the transparent sheet, as shown in FIGS. 54A and 54B, before and after the image recording process by the recording head 311, the punching processing unit 659 makes the transparent sheet transparent. It is possible to form pores in the sheet. Alternatively, as shown in FIGS. 53 (a) and 53 (b), before and after the transfer process by the laminating machine, pores may be formed in the transparent sheet by the perforating part 659. Further, the punching unit 659 may constitute a punching device that is independent from the printer unit and the transfer unit. In this case, in order to form pores in the state of the transfer material, it is preferable to provide an independent perforating portion as shown in FIG. 58 between the printer portion and the transfer portion. Further, in order to form pores after the substrate sheet is peeled off, it is preferable to provide an independent perforating part for perforating after the image transfer step as shown in FIG.

[5-9] Ninth Manufacturing Apparatus In a ninth configuration example (hereinafter also referred to as “ninth manufacturing apparatus”) of a recorded product manufacturing apparatus, the printer unit and the transfer unit are configured separately and independently. ing.

  In a manufacturing apparatus in which the printer unit and the transfer unit are integrated as shown in FIG. 13, when a serial type ink jet printer is used, there is a difference in the transfer speed of the transfer material and the image support between the print unit and the transfer unit. In order to absorb and adjust such a speed difference, it is necessary to make the transfer material and the image support slack. In the case of a separation type in which the print unit and the transfer unit are made independent, it is preferable because the processing in the print unit and the transfer unit can be carried out at the respective optimum speeds.

  FIG. 21A is a perspective view of a serial printer 501 that records an image on the transfer material 1, and the transfer material 1 is set in the supply unit 513. The transfer material 1 is transported to a recording position facing the recording head 502 by a transport roller 510, and is discharged after a reverse image is recorded. While moving the recording head 502 in the directions of arrows a and b, the nozzle 511 of the recording head 502 (the operation of ejecting ink from FIG. 21B) intersects the directions of arrows a and b (in this example, orthogonal). The image is recorded by repeating the operation of transporting the transfer material 1 in the direction in which the image is recorded.Then, the transfer material on which the image has been recorded and the image support are heat-pressed by the laminating machine of FIG. A recorded material is obtained by peeling off the base material sheet, and a recording guide is simultaneously recorded when an image is recorded on a transfer material, so that the image support 55 is visually confirmed to be along the bonding guide. However, they can be manually aligned.

  In the case where a transfer material that does not have a pore structure formed in advance is used for the transparent sheet, as shown in FIGS. It is possible to form pores in the sheet. Alternatively, as shown in FIGS. 53 (a) and 53 (b), before and after the transfer process by the laminating machine, pores may be formed in the transparent sheet by the perforating part 659. Further, the punching unit 659 may constitute a punching device that is independent from the printer unit and the transfer unit. In this case, in order to form pores in the state of the transfer material, it is preferable to provide an independent perforating portion as shown in FIG. 58 between the printer portion and the transfer portion. Further, in order to form pores after the substrate sheet is peeled off, it is preferable to provide an independent perforating part for perforating after the image transfer step as shown in FIG.

  In the first to ninth manufacturing apparatuses described above, in the step of attaching the transfer material to the image support when the transfer material has at least a transparent sheet and a color material receiving layer on the base material, Control of the ink moisture content of the receiving layer and temperature control at the time of adhesion are performed. Thereby, it is possible to improve the adhesion between the transparent sheet of the transfer material and the image support, and to provide a recorded material excellent in various durability such as weather resistance, water resistance, chemical resistance, and gas resistance. it can.

(Second invention)
Next, the second invention will be described.

[6] Transfer Material of Second Invention FIG. 68 is a sectional view of the transfer material 1 in the second invention. The transfer material 1 has a laminated structure in which a base sheet 50, a transparent sheet 52, and a color material receiving layer 53 are laminated in this order, and the transparent sheet 52 has a mechanism for draining water out of the system. The color material receiving layer 53 contains a water-soluble resin, and the transparent sheet 52 contains a swellable resin.

  60 is a cross-sectional view of a recorded matter 73 created by transferring the color material receiving layer 53 of the transfer material 1 and the transparent sheet 52 to the image support 55. FIG. Since the transparent sheet 52 has a swellable resin, it can absorb unnecessary moisture contained in the color material receiving layer 53 and evaporate from the surface as water vapor 550. 59 is a cross-sectional view of the recorded matter 73 in a state where the recorded matter 73 of FIG. 69 is immersed in water for a long time and then taken out from the water. When the recorded matter 73 is taken out of the water, the water absorbed in the color material receiving layer 53 evaporates not only from the end portion of the color material receiving layer 53 but also from the entire surface of the transparent sheet 52 through the swelling resin. In this way, by evaporating the water in the color material receiving layer from the entire surface of the transparent sheet, the shrinkage stress of the color material receiving layer is widely dispersed over the entire surface of the transparent sheet as indicated by the arrow B. As a result, The crack of a transparent sheet can be suppressed.

  Differences between the second invention and the first invention will be described. In the first invention, the transparent sheet has pores penetrating between the base material sheet and the color material receiving layer, and moisture of the color material receiving layer is exposed outside the system through the physical holes (pores). Discharged. In the first invention, there is a possibility that other molecules pass through the pores through which water passes. For example, ozone molecules. The size of gaseous water molecules is 0.4 nm, the size of ozone molecules is 0.44 nm, and ozone may pass if the pores are large enough to allow water to pass through. For this reason, the transparent sheet in the first invention may be slightly reduced in terms of gas resistance as compared to the nonporous transparent sheet in the second invention. However, by using a pigment having excellent weather resistance as a color material, a decrease in gas resistance is not a problem in practice.

  The transparent sheet in the second invention contains a swellable resin, and passes through the molecules of the swellable resin of the transparent sheet, not physical pores of the transparent sheet, and water is discharged out of the system. The Since the transparent sheet does not have through-holes, gases other than water do not easily pass through and are excellent in gas resistance. On the other hand, since the swellable resin contained in the transparent sheet also absorbs liquid water, when contaminated water or the like adheres to the surface of the transparent sheet for a long time, it is also absorbed from the surface of the transparent sheet. Therefore, compared with the transparent sheet in the first invention, the protection performance from liquid stains such as chemicals and contaminated water may be inferior. However, the water absorption rate in the transparent sheet containing the swellable resin is about several tenths of the water absorption rate in the void-absorbing type colorant receiving layer containing pores. Wiping off the stain will not lead to contamination of the colorant receiving layer.

  When manufacturing the recorded matter 73 according to the second invention, as shown in FIG. 70, first, the reverse image 72 is recorded on the color material receiving layer 53 of the transfer material 1 by the recording head 607 (step 1). Next, the transfer material 1 and the image support 55 are heat-pressed using the heat roller 21, and the color material receiving layer 53 is transferred to the image support 55 (step 2). Finally, the base material sheet 50 is peeled using the peeling roll 88 (step 3), thereby obtaining an ink jet recorded matter 73.

  As described above, the transfer material in the second invention has a laminated structure in which the base material sheet, the transparent sheet, and the color material receiving layer are laminated in this order, and the color material receiving layer contains a water-soluble resin, The transparent sheet contains a swellable resin.

[6-1] Color Material Receiving Layer As for the color material receiving layer, any of the swelling absorption type and void absorption type color material receiving layers can be used as in the first invention described above.

[6-1-1] Inorganic fine particles As the inorganic fine particles forming the colorant receiving layer, those similar to the above-mentioned [1-1-1] can be used.

[6-1-2] Water-soluble resin As the water-soluble resin for forming the colorant receiving layer, the same as [1-1-2] described above can be used.

[6-1-3] Cationic resin As the cationic resin for forming the colorant receiving layer, the same ones as described in [1-1-3] can be used.

[6-1-4] Other Additives As other additives for forming the colorant receiving layer, the same ones as described in [1-1-4] can be used.

[6-1-5] Thickness The thickness of the color material receiving layer can be set in the same manner as [1-1-5] described above.

[6-2] Transparent Sheet The transfer material 1 includes a transparent sheet 52 as shown in FIG. The transparent sheet 52 contains a swellable resin 660 and has a structure in which the swellable resin is uniformly dispersed from the colorant receiving layer 53 to the surface of the transparent sheet 52 and communicates therebetween. The swellable resin has a number of hydrophilic groups in the molecule, and has a property of absorbing water by capturing the water molecules 663 as shown in FIG. Therefore, even if the transparent sheet is nonporous, due to the presence of the swellable resin, the transparent sheet can absorb the excess moisture of the colorant receiving layer and evaporate from the surface. The transparent sheet newly absorbs moisture from the colorant receiving layer and evaporates it by the amount evaporated from the surface. That is, by adding a swellable resin to the transparent sheet, the transparent sheet can have a function as a pump for discharging moisture in the system of the recorded matter out of the system. As described above, when the swellable resin is contained in the transparent sheet, the swellable resin forms a passage through which moisture in the recorded matter can be released to the outside in the same manner as the pores. Therefore, when the recorded material is subjected to a water resistance test and a colorant receiving layer absorbs a large amount of water and then dried, the absorbed water is not only absorbed at the edges of the recorded material but also on the entire surface of the transparent sheet. It is also possible to suppress the occurrence of cracks caused by stress concentration by evaporating and evaporating from the substrate.

  In order for the transparent sheet to release moisture in the system to the outside of the system, it is preferable to include a swellable resin in all layers existing between the surface of the transparent sheet and the colorant receiving layer. For example, for the purpose of improving the smoothness of the surface of the transparent sheet or improving the adhesion with the colorant receiving layer, a layer is added to the base material sheet side or the colorant receiving layer side in the transparent sheet, A transparent sheet comprising a plurality of layers can also be used. In this case, in order for the transparent sheet to release moisture to the outside of the system, as shown in FIG. Necessary. If there is no water discharge mechanism between the transparent sheet and the colorant receiving layer, the discharge of water to the outside of the system is remarkably inhibited as shown in FIG. As a result, the amount of water evaporated from the surface of the transparent sheet is reduced, stress is concentrated on the transparent sheet, and cracks are likely to occur.

  Between the transparent coat and the colorant-receiving layer, an anchor layer for enhancing their adhesion or a hologram layer for enhancing security and design can be provided. In this case, as shown in FIGS. 62A and 62B, all the layers 161, 162, 58, and 59 of the transparent sheet existing from the surface of the transparent sheet to the colorant receiving layer have a water-soluble resin or It is preferable to contain a water absorbent resin.

[6-2-1] Thickness The thickness of the transparent sheet is not particularly limited. In addition to the water draining effect of the transparent sheet, the water resistance can be further improved by controlling the thickness of the transparent sheet relative to the thickness of the colorant receiving layer. That is, if the thickness of the transparent sheet is sufficiently larger than the thickness of the colorant receiving layer, the transparent sheet can absorb the shrinkage stress with sufficient strength, and thus the transparent sheet is hardly cracked. On the other hand, when the thickness of the transparent sheet becomes smaller than the thickness of the color material receiving layer, the strength of the transparent sheet becomes relatively weak and the shrinkage of the color material receiving layer becomes relatively large, so the crack of the transparent sheet occurs. It is necessary to increase the moisture permeability and water permeability of the transparent sheet. As will be described later, the degree of water permeability and moisture permeability can be controlled by the type of water-soluble resin, and in the case of polyvinyl alcohol, the degree of saponification and the degree of polymerization. The ratio (A / B) of the thickness (A) of the transparent sheet and the thickness (B) of the colorant receiving layer is preferably in the range of 0.07 ≦ (A / B) ≦ 3.00.0.

  If the ratio (A / B) is large and the thickness of the transparent sheet is sufficiently large relative to the thickness of the colorant receiving layer, the transparent sheet absorbs the shrinkage stress to some extent with sufficient strength. Cracks are unlikely to occur. Depending on the purpose of use of the recorded matter, it may be necessary to make the thickness of the transparent sheet, which is a protective layer, several tens of μm or more from the viewpoint of long-term storage stability, weather resistance, and security. Even in this case, depending on the adhesive force between the image support and the color material receiving layer and the adhesive force between the color material receiving layer and the transparent sheet, the water absorption expansion of the color material receiving layer containing the water-soluble resin and The stress can be relieved by setting the pore structure of the transparent sheet so as to correspond to the drying shrinkage. That is, when the transparent sheet is thick, the content of the swellable resin in the transparent sheet can be reduced. On the other hand, if the ratio (A / B) is small, the thickness of the transparent sheet is smaller than the thickness of the color material receiving layer, the strength of the transparent sheet is relatively weak, and the shrinkage of the color material receiving layer is relatively small. Since it becomes large, the transparent sheet is likely to crack. In this case, the water permeability and moisture permeability of the transparent sheet must be increased.

  Practically, the thickness of the transparent sheet is preferably 2 to 40 μm. By making the thickness of the transparent sheet more preferably 5 μm or more, the water resistance and scratch resistance of the transparent sheet can be further improved. On the other hand, if the thickness of the transparent sheet becomes too small, a large amount of energy is required for heat transfer at the time of thermocompression bonding to the recording support, and the evaporation of moisture from the colorant receiving layer via the swellable resin of the transparent sheet It becomes difficult to advance. Therefore, the thickness of the transparent sheet is desirably 40 μm or less. More preferably, by setting the thickness to 20 μm or less, in addition to the transparency and protection functions that are basic functions as a transparent sheet, it is easy to obtain a balance with incidental functions such as energy and moisture permeability during transfer adhesion. Become.

[6-2-2] Moisture permeability Since the recorded matter that has absorbed moisture is dried in about 30 minutes under normal circumstances, the moisture permeability of the transparent sheet should be (5 g / m ² · h) or more. In this case, the water resistance can be further improved. That is, by setting the moisture permeability of the transparent sheet to the above value or more, the stress at the time of contraction of the colorant receiving layer after water absorption is more widely dispersed, and the occurrence of cracks can be further suppressed.

[6-2-3] Swellable Resin Swellable resins include water-soluble resins that swell with water and dissolve in water, and water-absorbent resins that are insoluble in water.

  The water-soluble resin is a resin that is sufficiently mixed with water at 25 ° C. or a resin having a solubility in water of 1 (g / 100 g) or more. The kind of water-soluble resin is not particularly limited. For example, the same water-soluble resin as the colorant-receiving layer described in item [1-1-2] can be used. Among these, as the polyvinyl alcohol, complete saponification, partial saponification, low saponification and the like, or modified products thereof (cation modified product, anion modified product, silanol modified product, etc.) can be used particularly preferably. In particular, saponified polyvinyl alcohol obtained by hydrolyzing (saponifying) polyvinyl acetate is preferred. Saponified polyvinyl alcohol is also preferably used in the color material receiving layer described later, and by using saponified polyvinyl alcohol also in the transparent sheet, the adhesiveness (transfer performance) between the transparent sheet and the color material receiving layer may be improved. it can. In addition, acrylic, polyester-based, polyurethane-based, polyamide-based, nylon-based, or the like, which is a water-soluble resin by adding a hydrophilic group in the molecule, or a copolymer can also be used. The swellable resin is a swellable and water-insoluble resin having a water absorption capacity (CRC) of 0.1 g / g or more under no pressure. The total amount (100%) of the swellable resin is not limited to being a polymer, and may contain additives to be described later as long as the above performance is maintained. That is, in the present invention, the composition of the swellable resin containing the swellable resin and the additive is also collectively referred to as the swellable resin. The swelling resin is not particularly limited. For example, (meth) acrylate-based, (meth) acrylamide-based, vinyl alcohol-based, maleic anhydride (salt) -based, polyurethane-based alone or copolymer, (meth) acrylamide- (meth) acrylate Copolymer, sulfonic acid group-containing (meth) acrylate-based homopolymer or copolymer, vinyl acetate-maleic anhydride copolymer, vinyl acetate-acrylate copolymer, starch-based or cellulose-based polymer, Examples thereof include partially crosslinked polymers and graft-modified polymers.

  Swelling resin may be used individually by 1 type, or can mix and use 2 or more types. “Two or more” includes those having different characteristics such as saponification degree and average degree of polymerization.

[6-2-4] Amount of swellable resin The amount of the swellable resin is preferably 0.05% by mass or more and 2.00% by mass or less of the entire transparent sheet. More preferably, they are 0.09 mass% or more and 1.00 mass% or less, More preferably, they are 0.15 mass% or more and 0.60 mass% or less. A state in which the swellable resin is uniformly dispersed in the transparent sheet by setting the amount of the swellable resin to 0.05% by mass or more, preferably 0.09% by mass or more, and more preferably 0.15% by mass or more. In addition, the surface of the transparent sheet and the color material receiving layer are communicated with each other in a sufficient amount. As a result, more water can be evaporated from the surface of the transparent sheet, and the shrinkage stress can be widely dispersed, thereby suppressing the occurrence of cracks in the transparent sheet. In addition, the amount of the swellable resin is 2.00% by mass or less, preferably 1.00% by mass or less, more preferably 0.6% by mass or less, so that the mechanical strength of the transparent sheet can be improved by dissolution or excessive swelling. The generation of cracks in the transparent sheet can be suppressed without lowering the thickness. On the other hand, if the swellable resin is larger than 2.00% by mass, the mechanical strength of the transparent sheet is lowered, cracking is likely to occur due to shrinkage stress, and the scratching property may be lowered. Further, when the transparent sheet contains a particulate emulsion, if there is a large amount of the swellable resin, the swellable resin contributes to the dispersion of the emulsion, the emulsion particle size changes greatly, and the transparency of the transparent sheet decreases. There is a fear. Furthermore, the water absorption of the transparent sheet may be too high, and the liquid may be easily contaminated when it is stained with liquid. On the other hand, if the swellable resin is less than 0.05% by mass, moisture evaporation from the transparent sheet becomes insufficient, and cracking of the transparent sheet is likely to occur.

  If the swelling ratio of the swellable resin due to water absorption (hereinafter referred to as the water absorption swelling ratio) is too high, the recording sheet will be cracked in the transparent sheet due to the strain swelled in the transparent sheet when immersed in water. May be easy to enter.

In the present invention, considering the balance of the ratio of swelling of the swellable resin by water absorption, it is particularly preferable to contain polyvinyl alcohol (PVA) whose saponification degree and polymerization degree are strictly controlled as the swellable resin. PVA has a large amount of hydroxyl groups in the molecule, and these generate hydrogen bonds within the PVA molecule or between PVA molecules. When the degree of polymerization and the degree of saponification are high, since the polyvinyl alcohols are strongly bonded by more hydrogen bonds, the volume swollen by water absorption can be kept low.
In addition, polyvinyl alcohol having a high polymerization degree and a high saponification degree is effective in improving the scratch resistance of the transparent sheet because it becomes a hard resin among water-soluble resins due to hydrogen bonding in the molecule. Furthermore, polyvinyl alcohol is also preferably used in the color material receiving layer, and the adhesiveness with the color material receiving layer can also be improved by including polyvinyl alcohol in the transparent sheet.

  Here, when the swellable resin of the transparent sheet absorbs a large amount of water, there is a possibility that the protection performance due to the liquid stain is slightly lowered. That is, as shown in FIG. 63, when liquid dirt such as contaminated water 552 adheres to the surface of the transparent sheet 52, the swellable resin of the transparent sheet 52 absorbs the contaminated water 552, and the contaminated water 552 There is a risk of being absorbed by contact with the colorant receiving layer 53. When the contaminated water 552 is colored, the recorded information by the reverse image 72 is colored by the liquid water 552 from the background side, and a part of the recorded information may disappear.

  However, by containing polyvinyl alcohol having a high saponification degree and a high polymerization degree in a preferable range, it is possible to suppress a decrease in protective performance. In the case of polyvinyl alcohol having a high degree of saponification and a high degree of polymerization, the amount of hydrogen bonds between the polyvinyl alcohols is large, and it takes a very long time to hydrate water. Therefore, when the contaminated water 552 adheres to the surface of the transparent sheet 52 as shown in FIG. 64, the absorption rate of the contaminated water is also suppressed, so that the contamination hardly spreads in the transparent sheet 52 and the colorant receiving layer 53.

[6-2-5] Polyvinyl alcohol saponification degree and polymerization degree The polyvinyl alcohol used for the transparent sheet is preferably composed of a composition containing polyvinyl alcohol having a saponification degree of 75 to 100 mol%.

  By setting the degree of saponification to preferably 86 mol% or more, more preferably 98 mol% or more, the amount of polyvinyl alcohol that swells due to water absorption can be optimized, and moisture can be evaporated from the surface of the transparent sheet to generate cracks. It can be suppressed more. Furthermore, the moisture absorption rate can be suppressed to prevent contamination of recorded information from liquid stains. If it is less than 86 mol%, the amount of swelling due to the water absorption of polyvinyl alcohol when the recorded material is immersed in water becomes large, so that cracking tends to occur. In addition, the moisture absorption rate is increased, and contamination with liquid stains is likely to occur. Further, the strength of the polyvinyl alcohol is lowered, and the scratchability of the transparent sheet may be lowered.

  As saponified polyvinyl alcohol satisfying the range of saponification degree, completely saponified polyvinyl alcohol (saponification degree 98-100 mol%), partially saponified polyvinyl alcohol (saponification degree 87-89 mol%), low saponified polyvinyl alcohol (saponification degree 78-82 mol%). And the like. Of these, completely saponified polyvinyl alcohol is preferred.

  The transparent sheet is preferably made of a composition containing polyvinyl alcohol having an average degree of polymerization of 1,500 to 5,000.

  By making the average degree of polymerization preferably 1,500 or more, more preferably 2,000 or more, it is possible to optimize the amount of polyvinyl alcohol swelled by water absorption, evaporate moisture from the surface of the transparent sheet, The occurrence of cracks can be further suppressed. Furthermore, the moisture absorption rate can be suppressed to prevent contamination of recorded information from liquid stains. On the other hand, by making the average degree of polymerization preferably 5,000 or less, more preferably 4,500 or less, the transparent sheet is not excessively hardened, and cracking is less likely to occur when the transparent sheet is stressed. be able to. The average degree of polymerization is a value calculated according to the method described in JIS-K-6726. If the average degree of polymerization is less than 1500, the amount of swelling due to water absorption of polyvinyl alcohol when the recorded material is immersed in water becomes large, so that cracking is likely to occur. In addition, the moisture absorption rate is increased, and contamination with liquid stains is likely to occur. Further, the strength of the polyvinyl alcohol is lowered, and the scratchability of the transparent sheet may be lowered. When the average degree of polymerization is greater than 5000, the amount of hydrogen bonds in the polyvinyl alcohol molecule increases, so that it becomes difficult to swell due to water absorption, and the action as a pump for discharging water is reduced, so that stress is applied to the transparent sheet. There is a risk of cracking when applied.

[6-2-6] Emulsion As the emulsion constituting the transparent sheet, the same as [1-2-4] described above can be used.

[6-2-7] Thickness The thickness of the transparent sheet is not particularly limited, and those similar to [1-2-2] described above can be used. However, in the second invention, the ratio (A / B) between the thickness (A) of the transparent sheet and the thickness (B) of the colorant receiving layer is preferably in the range of the following formula (1).
0.07 ≦ (A / B) ≦ 3.00 (1)
If A / B is 0.07 or more, the thickness of the transparent sheet is sufficiently large with respect to the thickness of the colorant receiving layer and has sufficient strength, so that even if water permeability and moisture permeability are small, cracks are unlikely to occur. . Moreover, if A / B is 3.00 or less, the thickness of the transparent sheet is smaller than the thickness of the color material receiving layer, and heat conduction can be improved when thermocompression bonding is performed. Adhesiveness (transfer performance) with the layer can be improved. On the other hand, when A / B is smaller than 0.07, the thickness of the transparent sheet is small relative to the thickness of the color material receiving layer and does not have sufficient strength to withstand the shrinkage of the color material receiving layer. Cracks tend to occur when moisture permeability is low. Further, when A / B is larger than 3, the thickness of the transparent sheet becomes larger than the thickness of the color material receiving layer, and the heat conduction is lowered when heat-pressing, and the transfer performance between the transparent sheet and the color material receiving layer. Decreases.

  As described above, if the ratio (A / B) is large and the thickness of the transparent sheet is sufficiently large with respect to the thickness of the colorant receiving layer, the transparent sheet has sufficient strength and absorbs the shrinkage stress to some extent. Therefore, cracks are unlikely to occur in the transparent sheet.

[6-3] Base sheet The same base sheet as described in [1-3] can be used.

[6-4] Release Sheet As the release sheet, the same as [1-4] described above can be used.

[6-4] Anchor layer As the anchor layer, those similar to the above-mentioned [1-5] can be used. However, in the second invention, since the transparent sheet releases moisture out of the system, the anchor layer 59 needs to contain a swellable resin as shown in FIG.

[6-6] Hologram Layer As the hologram layer, the same as [1-6] described above can be used. However, in the second invention, since the transparent sheet releases moisture out of the system, the hologram layer 58 needs to contain a swellable resin as shown in FIG.

[6-7] Laminated Structure The transfer material 1 has a laminated structure in which a base sheet 50, a transparent sheet 52, and a color material receiving layer 53 are sequentially laminated as shown in FIG. “Substrate sheet, transparent sheet and color material receiving layer are sequentially laminated” means that the base sheet, transparent sheet, color material receiving layer, regardless of whether or not other layers are interposed, It means that the transparent sheet and the color material receiving layer are laminated according to the order. That is, the structure in which the anchor layer 59 and the hologram layer 58 exist between the transparent sheet 52 and the color material receiving layer 53 as in the transfer material 1 in FIGS. , A transparent sheet and a colorant-receiving layer are included in the laminated structure.

  As shown in FIG. 68, the transfer material 1 preferably has a laminated structure in which a base sheet 50, a transparent sheet 52, and a color material receiving layer 53 are in contact with each other. That is, a structure in which no other layer (including a sheet) is interposed between the base sheet 50 and the transparent sheet 52 and between the transparent sheet 52 and the color material receiving layer 53 is preferable. This is because the thickness of a credit card or the like, which is an object of the recorded material, is strictly limited, so that it is desirable to reduce the number of layers and sheets to be stacked to reduce the thickness of the recorded material.

  When the transfer material further includes a release layer 51, an anchor layer 59, and a hologram layer 58, the color material receiving layer 53, the anchor layer 59, the hologram layer 58, the transparent sheet 52, the release layer 51, and the base material sheet 50 are provided. A stacked structure in which layers are sequentially stacked is preferable.

[6-8] Shape and thickness of transfer material The shape and thickness of the transfer material can be set in the same manner as [1-8] described above.

[6-9] Manufacturing Method The transfer material can be manufactured by the same method as [1-9] described above. That is, a coating liquid containing a water-soluble resin or a water-absorbing resin for forming a transparent sheet is applied to the base sheet, and the transparent sheet is laminated on the base sheet. Thereafter, a transfer material can be produced by coating the laminate with a coating solution containing at least a water-soluble resin. In addition, when setting it as a space | gap absorption type structure, a transfer material can be manufactured by applying the coating liquid containing an inorganic fine particle, water-soluble resin, and cationic resin at least.

[6-10] Image As the image, the same image as [1-10] described above can be recorded.

[6-11] Image Recording Image recording can be performed in the same manner as [1-11] described above.

[6-12] Primer layer As the primer layer, those similar to [1-12] described above can be used.

[7] Recorded matter The recorded matter in the second invention is a recorded matter comprising an image support, a colorant receiving layer, and a transparent sheet as shown in FIG. An image is recorded on a color material receiving layer of a transfer material in which a base material sheet, a transparent sheet, and a color material receiving layer containing at least a swellable resin are laminated, and then the transfer material is laminated on an image support. Then, the recorded material is obtained by peeling the substrate sheet. The transfer material (recording medium) on which the image is recorded is obtained by the transfer material described in [6] above.

[8] Method for Producing Recorded Material in Second Invention The recorded material in the second invention is produced through steps 5, 6, and 7 as shown in FIG. In step 5, an image is recorded on the color material receiving layer of the transfer material described in [6] above to obtain a recording medium. In step 6, the color material receiving layer of the recording medium is heated and pressure-bonded to an image support, In 7, the base sheet is peeled off.

[8-1] Image support As the image support, the same one as described in [3-1] can be used.

[8-2] Laminated Structure The recorded matter has a laminated structure in which the image support 55, the color material receiving layer 53, and the transparent sheet 52 are sequentially laminated in the same manner as the recorded matter 73 in FIG.

[8-3] Thermocompression bonding between the transfer material and the image support The thermocompression bonding between the transfer material and the image support can be performed in the same manner as [3-3] using the manufacturing apparatus 25 of FIG.

[8-4] Peeling of base material sheet and release layer The recorded material is peeled off the base material sheet 50 in the same manner as the recorded material 73 of FIG. 53 and a transparent sheet 52 are sequentially laminated. The base material sheet 50 can be peeled in the same manner as [3-4] described above.

[8-5] Double-sided simultaneous peeling Double-sided simultaneous peeling can be carried out in the same manner as [3-5] described above.

[9] Recording apparatus in the second invention As shown in FIG. 65, the recording apparatus in the second invention is a supply unit 4 for feeding the transfer material 1 described in [6] above to the transport path, and the transfer material 1 And a recording unit 6 for recording an image by applying a color material to the color material receiving layer. As the recording apparatus, the same recording apparatus as described in [4-1] can be used.

[10] Recorded matter manufacturing apparatus according to the second aspect [7] The recorded matter manufacturing apparatus of [7] described above, the recording device according to [9] described above, a supply unit for feeding the image support to the conveyance path, An attachment portion for attaching the recording medium to the image support and a peeling portion for peeling the base sheet from the recording medium are provided.

[10-1] Tenth Manufacturing Apparatus The tenth manufacturing apparatus can be configured in the same manner as the first manufacturing apparatus 25 in FIG. 9 or FIG. 13 described above. It differs from the first manufacturing apparatus only in that a transfer material containing a swellable resin capable of releasing moisture out of the system is used.

[10-2] Eleventh Manufacturing Apparatus In the eleventh manufacturing apparatus, similarly to the above-described sixth manufacturing apparatus, the printer unit and the transfer unit are configured separately and independently. It differs from the sixth manufacturing apparatus only in that a roll-shaped transfer material containing a swellable resin capable of releasing moisture out of the system is used.

[10-3] Twelfth Manufacturing Apparatus In the twelfth manufacturing apparatus, similarly to the seventh manufacturing apparatus described above, the printer unit and the transfer unit are configured separately and independently. It differs from the seventh manufacturing apparatus only in that a roll-shaped transfer material containing a swellable resin capable of releasing moisture out of the system is used.

[10-4] Thirteenth Manufacturing Apparatus In the thirteenth manufacturing apparatus, similarly to the above-described eighth manufacturing apparatus, the printer unit and the transfer unit are configured separately and independently. It differs from the eighth manufacturing apparatus only in that a roll-shaped transfer material containing a swellable resin capable of releasing moisture out of the system is used.

[10-5] Fourteenth Manufacturing Apparatus In the fourteenth manufacturing apparatus, similarly to the ninth manufacturing apparatus described above, the printer unit and the transfer unit are configured separately and independently. It differs from the ninth manufacturing apparatus only in that a roll-shaped transfer material containing a swellable resin capable of releasing moisture out of the system is used.

  In the above tenth to fifteenth manufacturing apparatuses, when the transfer material has at least a transparent sheet containing a swellable resin and a color material receiving layer on the base material, the transfer material is used as an image support. In the adhering step, control of the ink moisture content of the color material receiving layer and temperature control during adhering are performed. Thereby, it is possible to improve the adhesion between the transparent sheet of the transfer material and the image support, and to provide a recorded material excellent in various durability such as weather resistance, water resistance, chemical resistance, and gas resistance. it can.

  Hereinafter, specific examples of the present invention will be described. However, the present invention is not limited in any way by the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Example 1
[Synthesis of coating liquid for forming transparent sheet]
9 parts of an acrylic emulsion aqueous solution (BASF Co., Ltd. Jonkrill 352D, Tg 56 ° C., solid content concentration 45%) and urethane emulsion aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 130, Tg 101 ° C., solid content concentration 35%) 1 part And stirring and mixing for 5 minutes to obtain a coating solution for laminated sheets.

[Manufacture of laminated sheets (component materials for transfer materials)]
A transfer containing a transparent sheet on which no pores are formed and a base sheet by applying a coating liquid for forming a transparent sheet on the surface (thickness 25 μm) of the PET base sheet and drying it. A laminated sheet as a constituent material of the material was manufactured. A die coater was used for coating, the coating speed was 5 m / min, and the coating amount after drying was 5 g / m ² . The drying temperature was 90 ° C. The thickness (B) of the transparent sheet was 5 μm.

[Formation of pores]
The laminated sheet was mechanically perforated by the pore formation method (a) in FIG. 60 to produce a transfer material including a transparent sheet having pores formed therein. A needle 657 as shown in FIG. 46A was used for the drilling process. The distribution density of the pores was such that one pore per square mm was present, and the pore diameter was 0.02 μm. For the layer in which the pores are formed (the protective sheet (transparent sheet) in Example 1), the passage locations in the table are circled. If the circle is not shown in the table, it indicates that no pores are formed in the layer.

[Preparation of Alumina Hydrate Dispersion]
20 parts of alumina hydrate A having a boehmite structure (pseudo boehmite structure) (trade name “Disperal HP14”, manufactured by Sasol) is added to pure water, and 0.4 part of acetic acid is further added to perform peptization. As a result, an alumina hydrate dispersion was obtained. The average particle diameter of the alumina hydrate fine particles in the alumina hydrate dispersion was 140 nm. Next, 0.3 parts of boric acid was added to the dispersion to obtain a boric acid-added alumina hydrate dispersion.

[Preparation of aqueous polyvinyl alcohol solution]
Polyvinyl alcohol (trade name “PVA235”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare a polyvinyl alcohol aqueous solution having a solid content of 8%. Polyvinyl alcohol had an average degree of polymerization of 3,500, a degree of saponification of 87 to 89 mol%, and an SP value of 9.4.

[Preparation of coating solution for forming colorant receiving layer]
Add 27.8 parts of polyvinyl alcohol aqueous solution to 100 parts of boric acid-added alumina hydrate dispersion, and then add 3.0 parts of polyallylamine as a cationic resin and mix with a static mixer to form a colorant receiving layer. A coating solution was obtained. As the polyallylamine, polyallylamine (trade name “PAA-01”, manufactured by Nittobo) having a melting point of 83.3 ° C. and an average degree of polymerization of 1,600 was used.

[Manufacture of transfer material]
On the surface of the transparent sheet of the laminated sheet in which the pores were formed, a coating material for forming a color material receiving layer immediately after mixing was applied and dried to provide a void absorption type color material receiving layer A transfer material was produced. A die coater was used for coating the coating solution, the coating speed was 5 m / min, and the coating amount after drying was 15 g / m ² . The drying temperature was 60 ° C. The transfer material was made into a roll-shaped transfer material by winding in a roll shape with the color material receiving layer on the outside and the base material sheet on the inside. The thickness A of the colorant receiving layer was 10 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.5.

[Measurement of moisture permeability]
The moisture permeability of the transparent sheet of the transfer material was measured by the method defined in JIS L1099B-2. The moisture permeability of the transparent sheet was 10 g / m ² · h.

  A 60% solid image with a recording duty of 60% was recorded with the pigment ink on the transfer material of Example 1 thus obtained using the first manufacturing apparatus described above. Then, the recorded material of Example 1 was obtained by heat-pressing the transfer material on the image support and then peeling the substrate sheet. The method for preparing the pigment ink will be described later. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”). The thermocompression bonding conditions were a temperature of 160 ° C., a pressure of 3.9 Kg / cm, and a conveyance speed of 50 mm / sec. The peeling angle when peeling the base sheet was 90 °. The difference SP2 between the SP value of the color material receiving layer and the SP value of the image support was 0.1.

[Preparation of pigment ink]
<Synthesis of (meth) acrylic ester copolymer>
1,000 parts of methyl ethyl ketone was charged into a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introducing device at the top, and the inside of the reaction vessel was purged with nitrogen while stirring the methyl ethyl ketone. did. The temperature inside the reaction vessel was raised to 80 ° C. while maintaining a nitrogen atmosphere, and then from a dropping device, 63 parts of 2-hydroxyethyl methacrylate, 141 parts of methacrylic acid, 417 parts of styrene, 188 parts of benzyl methacrylate, and 25 parts of glycidyl methacrylate. , 33 parts of a polymerization degree modifier (trade name “Blenmer TGL”, manufactured by NOF Corporation) and 67 parts of peroxy-2-ethylhexanoic acid-t-butyl were added dropwise over 4 hours. . After completion of the dropwise addition, the reaction was further continued at the same temperature for 10 hours, and a (meth) acrylic acid ester copolymer (A) having an acid value of 110 mgKOH / g, a glass transition point (Tg) of 89 ° C., and a weight average molecular weight of 8,000 (A -1) solution (resin content: 45.4%).

<Preparation 1 of aqueous pigment dispersion>
In a mixing tank equipped with a cooling function, 1,000 parts of a phthalocyanine blue pigment, a solution of the (meth) acrylic ester copolymer (A-1) obtained by the above synthesis, a 25% aqueous potassium hydroxide solution, And water were charged, stirred and mixed to obtain a mixed solution. The (meth) acrylic acid ester copolymer (A-1) was used in an amount of 40% in terms of nonvolatile content with respect to the phthalocyanine blue pigment. Moreover, as 25% potassium hydroxide aqueous solution, the quantity by which (meth) acrylic acid ester type copolymer (A-1) is neutralized 100% was used. Furthermore, the water used the quantity which makes the non volatile matter of the obtained liquid mixture 27%. The obtained mixed solution was passed through a dispersing apparatus filled with zirconia beads having a diameter of 0.3 mm, and dispersed for 4 hours by a circulation method. The temperature of the dispersion was kept below 40 ° C.

  After the dispersion liquid was extracted from the mixing tank, the flow path between the mixing tank and the dispersion apparatus was washed with 10,000 parts of water, and the cleaning liquid and the dispersion liquid were mixed to obtain a diluted dispersion liquid. The obtained diluted dispersion was put into a distillation apparatus, and the whole amount of methyl ethyl ketone and a part of water were distilled off to obtain a concentrated dispersion. 2% hydrochloric acid was added dropwise with stirring to the concentrated dispersion which had been allowed to cool to room temperature, and the pH was adjusted to 4.5. Then, the solid content was filtered and washed with a Nutsche filter. The obtained solid (cake) was put in a container, water was added, and then redispersed using a dispersion stirrer, and the pH was adjusted to 9.5 with a 25% aqueous potassium hydroxide solution. Thereafter, using a centrifugal separator, coarse particles were removed at 6000 G for 30 minutes, and then the non-volatile content was adjusted to obtain an aqueous cyan pigment dispersion (pigment content: 14% acid value 110).

  Except for changing the phthalocyanine blue pigment to carbon black black pigment, quinacridone magenta pigment or diazo yellow pigment, the same as the aqueous cyan pigment dispersion, the aqueous black pigment dispersion, the aqueous magenta pigment dispersion Or an aqueous yellow pigment dispersion was obtained.

<Preparation of ink>
The aqueous pigment dispersion and each component shown in Table 3 were put into a container so as to have the composition shown in Table 3 below (total: 100 parts), and stirred for 30 minutes or more using a propeller stirrer. Thereafter, the mixture was filtered with a filter having a pore size of 0.2 μm (manufactured by Nippon Pole Co., Ltd.) to prepare pigment ink. “AE-100” in Table 3 represents an acetylene glycol 10-mole ethylene oxide adduct (trade name “acetylenol E100”, manufactured by Kawaken Fine Chemicals).

(Example 2)
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the coating material for forming the color material receiving layer was changed to NS625XC made of Takamatsu Oil and Fat and a swollen color material receiving layer was formed. The pore diameter, moisture permeability, and thickness ratio A / B in Example 2 are shown in Table 4 described later.

(Example 3)
A transfer material and recorded matter were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 0.002 μm. The moisture permeability and thickness ratio A / B in Example 3 are shown in Table 4 described later.

(Example 4)
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 0.7 μm. The moisture permeability and thickness ratio A / B in Example 4 are shown in Table 4 described later.

(Example 5)
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 0.001 μm. The moisture permeability and thickness ratio A / B in Example 5 are shown in Table 4 described later.

(Example 6)
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 1 μm. The moisture permeability and thickness ratio A / B in Example 6 are shown in Table 4 described later.

(Example 7)
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 10 μm. The moisture permeability and thickness ratio A / B in Example 7 are shown in Table 4 described later.

(Example 8)
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the pore diameter of the transparent sheet was changed from 0.02 μm to 100 μm. The moisture permeability and thickness ratio A / B in Example 8 are shown in Table 4 described later.

Example 9
A transfer material and recorded matter were obtained in the same manner as in Example 1 except that the pore distribution density of the transparent sheet was changed from 1 hole per 1 square mm to 1 hole per 5 square mm. The pore diameter, moisture permeability, and thickness ratio A / B in Example 3 are shown in Table 4 described later.

(Example 10)
A transfer material and recorded matter were obtained in the same manner as in Example 1 except that the pore distribution density of the transparent sheet was changed from 1 hole per square mm to 1 hole per 10 square mm. The moisture permeability was 2 g / m ² · h. The pore diameter and thickness ratio A / B in Example 3 are shown in Table 4 described later.

(Example 11)
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the thickness A of the transparent sheet was changed from 5 μm to 15 μm and the thickness of the colorant receiving layer was changed from 10 μm to 5 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 3.

Example 12
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the thickness A of the transparent sheet was changed from 5 μm to 1 μm and the thickness B of the colorant receiving layer was changed from 10 μm to 15 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.07.

(Example 13)
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the thickness A of the transparent sheet was changed from 5 μm to 20 μm and the thickness of the colorant receiving layer was changed from 10 μm to 5 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 4.

(Example 14)
A transfer material and a recorded material were obtained in the same manner as in Example 1 except that the thickness A of the transparent sheet was changed from 5 μm to 0.5 μm and the thickness of the colorant receiving layer was changed to 0.5 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.03.

(Example 15)
[Manufacture of laminated sheets (component materials for transfer materials)]
As a film having a pore structure, a waterproof and moisture-permeable film having a thickness of 5 μm formed by combining an ePTFE film obtained by stretching polytetrafluoroethylene (PTFE) and a polyurethane polymer is used as a PET base sheet (thickness). 25 μm) to produce a laminated sheet. The transparent sheet of the laminated sheet includes 1.4 billion fine holes per square centimeter, and is compatible with waterproofness and moisture permeability. The water pressure resistance is 45000 mm or more, and the moisture permeability is 13500 g / m2 / 24 hrs as measured by the JIS L1099B-2 method.

[Manufacture of transfer material]
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the laminated sheet was changed.

(Example 16)
[Manufacture of laminated sheets (component materials for transfer materials)]
As a transparent film having a pore structure, a waterproof and moisture-permeable film having a thickness of 5 μm prepared by craze processing of polyvinylidene fluoride was laminated on a PET base sheet (thickness: 25 μm) to produce a laminated sheet. The transparent sheet of the laminated sheet includes 400 million fine holes in one square centimeter, and can achieve both waterproofness and moisture permeability. Moisture permeability is 3800g / m ² / 24hrs as measured by JIS L1099B-2 method.

[Manufacture of transfer material]
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the laminated sheet was changed.

(Example 17)
[Synthesis of coating solution for forming transparent sheet]
9 parts of an acrylic emulsion aqueous solution (BASF Co., Ltd. Jonkrill 352D, Tg 56 ° C.), a urethane emulsion aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 130, Tg), and 1 part of a foaming agent were added to add 5 parts. The mixture was stirred and mixed to obtain a coating solution for a laminated sheet.

[Manufacture of laminated sheets]
A transparent sheet-forming coating solution was applied to the surface (thickness 25 μm) of the PET base sheet by the method described in FIG. 55 (C), and then dried to produce a laminated sheet. A die coater was used for the coating, the coating speed was 5 m / min, and the coating amount after drying was 5 g / m ² . The drying temperature was 90 ° C. The thickness B of the transparent sheet was 5 μm. The distribution density of the pores was a density where 10,000 pores exist per square mm, and the pore diameter was 0.02 μm. The moisture permeability was 10 g / m ² · h.

[Manufacture of transfer material]
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the laminated sheet was changed.

(Example 18)
[Synthesis of coating solution for forming transparent sheet]
9 parts of an acrylic emulsion aqueous solution (BASF Co., Ltd. Jonkrill 352D, Tg56 ° C.), 1 part of urethane emulsion aqueous solution (Daiichi Kogyo Seiyaku Superflex 130, Tg), 1 part of porous resin particles, In addition, the mixture was stirred and mixed for 5 minutes to obtain a coating liquid for forming a transparent sheet.

[Manufacture of laminated sheets]
By applying the coating liquid for forming a transparent sheet to the surface (thickness 25 μm) of the PET base sheet by the method described in FIG. 37 (c), the laminate sheet was manufactured by drying. A die coater was used for the coating, the coating speed was 5 m / min, and the coating amount after drying was 5 g / m ² . The drying temperature was 90 ° C. The thickness B of the transparent sheet was 5 μm. The distribution density of the pores was a density in which 10,000 pores exist per square mm, and the pore diameter was 0.02 μm. The moisture permeability was 10 g / m ² · h.

[Manufacture of transfer material]
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the laminated sheet was changed.

(Example 19)
[Synthesis of coating solution for forming transparent sheet]
Add 9 parts of an acrylic emulsion aqueous solution (BASF Co., Ltd. Joncrill 352D, Tg56 ° C), 1 part of urethane emulsion aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 130, Tg), and 1 part of hollow resin particles. For 5 minutes to obtain a coating solution for forming a transparent sheet.

[Manufacture of laminated sheets]
By applying the coating liquid for forming the transparent sheet to the surface (thickness 25 μm) of the PET base sheet by the method described in FIG. 38 (c), the laminate sheet was manufactured by drying. A die coater was used for the coating, the coating speed was 5 m / min, and the coating amount after drying was 5 g / m ² . The drying temperature was 90 ° C. The thickness B of the transparent sheet was 5 μm. The distribution density of the pores was such that one pore was present per 4 mm 2, and the pore diameter was 0.02 μm. The moisture permeability was 10 g / m ² · h.

[Manufacture of transfer material]
A transfer material and a recorded matter were obtained in the same manner as in Example 1 except that the laminated sheet was changed.

(Example 20)
The transfer material and recorded matter are the same as in Example 1 except that the punching method is changed from the method using the needle 657 as shown in FIG. 46A to the method using the spur 650 as shown in FIG. 46B. Got.

(Example 21)
Except for changing the perforation processing method from the method using the needle 657 as shown in FIG. 46 (a) to the method using the laser processing device 658 as shown in FIG. 46 (c), the transfer material and A record was obtained.

(Example 22)
Except for changing the formation method of the pores from the method described in FIG. 41A to the description in FIG. 42A, pores were formed in the transparent sheet and the base sheet in the same manner as in Example 1. The formed laminated sheet was manufactured. Using the stacked sheets, transfer materials and recorded matter were obtained in the same manner as in Example 1.

(Example 23)
Except for changing the formation method of the pores from the method shown in FIG. 41A to the description shown in FIG. 40A, pores were formed in the transparent sheet and the colorant receiving layer in the same manner as in Example 1. A laminated sheet in which was formed was manufactured. Using the stacked sheets, transfer materials and recorded matter were obtained in the same manner as in Example 1.

(Example 24)
A transparent sheet, a colorant receiving layer, and a substrate were formed in the same manner as in Example 1 except that the pore formation method was changed from the method shown in FIG. 41 (a) to the one shown in FIG. 42 (b). A laminated sheet in which pores were formed in the sheet was produced. Using the stacked sheets, transfer materials and recorded matter were obtained in the same manner as in Example 1.

(Example 25)
[Manufacture of transfer material 25]
A transfer material was obtained in the same manner as in Example 1 except that pore formation was not performed on the laminated sheet.

[Manufacture of recorded materials]
Using the above-described second manufacturing apparatus (manufacturing apparatus in FIG. 28), the transfer material 25 is mechanically perforated in the stage before image recording to form pores in the base sheet and the transparent sheet. Thereafter, a 60% solid image with a recording duty of 60% was recorded with the pigment ink. Thereafter, the transfer material was heated and pressure-bonded to the image support, and then the base material sheet was peeled to obtain a recorded matter. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”).

(Example 26)
[Manufacture of recorded materials]
Using the above-described third manufacturing apparatus (manufacturing apparatus in FIG. 29), a 60% solid image with a recording duty of 60% is recorded on the transfer material 25 with pigment ink, and a mechanical perforation process is performed at a later stage. Pores were formed in the base sheet and the transparent sheet. Thereafter, the transfer material was heated and pressure-bonded to the image support, and then the substrate sheet was peeled off to obtain a recorded matter. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”).

(Example 27)
[Manufacture of recorded materials]
Using the above-described fourth manufacturing apparatus (manufacturing apparatus in FIG. 30), a 60% solid image with a recording duty of 60% was recorded on the transfer material 25 with pigment ink, and the transfer material was heat-pressed to the image support. . At a later stage, a mechanical perforation treatment was performed to form pores in the base sheet and the transparent sheet, and then the base sheet was peeled to obtain a recorded matter. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”).

(Example 28)
[Manufacture of recorded materials]
Using the above-described fifth manufacturing apparatus (manufacturing apparatus in FIG. 31), a 60% solid image with a recording duty of 60% is recorded on the transfer material 25 with pigment ink, and the transfer material is heated and pressure-bonded to the image support. From this, the base sheet was peeled off. When the substrate sheet was peeled off, a mechanical punching process was performed to form pores in the transparent sheet to obtain a recorded matter. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”).

(Example 29)
[Synthesis of PVA aqueous solution 1]
Polyvinyl alcohol (trade name “PVA123”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare a polyvinyl alcohol aqueous solution having a solid content of 8%. Polyvinyl alcohol had an average polymerization degree of 2300 and a saponification degree of 98 to 99 mol%.

[Synthesis of PVA aqueous solution 2]
Polyvinyl alcohol (trade name “PVA235”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare an aqueous polyvinyl alcohol solution having a solid content of 8%. Polyvinyl alcohol had an average polymerization degree of 3500 and a saponification degree of 87 to 89 mol%.

[Synthesis of PVA aqueous solution 3]
Polyvinyl alcohol (trade name “PVA117”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare a polyvinyl alcohol aqueous solution having a solid content of 8%. Polyvinyl alcohol had an average polymerization degree of 1700 and a saponification degree of 98 to 99 mol%.

[Synthesis of PVA aqueous solution 4]
Polyvinyl alcohol (trade name “PVA110”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare a polyvinyl alcohol aqueous solution having a solid content of 8%. Polyvinyl alcohol had an average degree of polymerization of 1100 and a degree of saponification of 98 to 99 mol%.

[Synthesis of PVA aqueous solution 5]
Polyvinyl alcohol (trade name “PVA424H”, manufactured by Kuraray Co., Ltd.) was dissolved in ion-exchanged water to prepare a polyvinyl alcohol aqueous solution having a solid content of 8%. Polyvinyl alcohol had an average degree of polymerization of 2400 and a degree of saponification of 78.5 to 80.5 mol%.

[Synthesis of coating solution for forming transparent sheet]
9 parts of an acrylic emulsion aqueous solution (BASF Co., Ltd. Jonkrill 352D, Tg 56 ° C., solid content concentration 45%) and urethane emulsion aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 130, Tg 103 ° C., solid content concentration 35%) 1 Part and 0.5 part of PVA aqueous solution 1 were added and mixed with stirring for 5 minutes to obtain a coating liquid for forming a transparent sheet. The content of the swellable resin is shown in Table 6.

[Manufacture of laminated sheets (component materials for transfer materials)]
After the coating liquid for forming the transparent sheet was applied to the surface (thickness 25 μm) of the PET base sheet, it was dried to produce a laminated sheet. A die coater was used for the coating, the coating speed was 5 m / min, and the coating amount after drying was 5 g / m ² . The drying temperature was 90 ° C.

[Manufacture of transfer material]
The transfer material of Example 1 provided with a void-absorbing color material receiving layer by applying a coating liquid for forming a color material receiving layer immediately after mixing to the surface of the transparent sheet in the laminated sheet and drying it. Manufactured. A die coater was used for coating the coating solution, the coating speed was 5 m / min, and the coating amount after drying was 15 g / m ² . The drying temperature was 60 ° C. The transfer material was made into a roll-shaped transfer material by winding in a roll shape with the color material receiving layer on the outside and the base sheet on the inside. The thickness A of the colorant receiving layer was 10 μm. The ratio A / B between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.5.

  A 60% solid image with a recording duty of 60% is recorded on the transfer material obtained as described above with the pigment ink using the first manufacturing apparatus described above, and the transfer material is heated and pressure-bonded to the image support. Then, the recorded material was obtained by peeling the base sheet. As a recording unit of the manufacturing apparatus, a print module (trade name “PM-200Z”, manufactured by Canon Finetech) equipped with a line head is used, and a card made of vinyl chloride (trade name “C-4002” is used as an image support. “Evolis”). The thermocompression bonding conditions are a temperature of 160 ° C., a pressure of 3.9 Kg / cm, and a conveyance speed of 50 mm / sec. The peeling angle when peeling the base sheet was 90 °. The difference SP2 between the SP value of the color material receiving layer and the SP value of the image support was 0.1.

(Example 30)
A transfer material and a recorded material were obtained in the same manner as in Example 29 except that the coating material for forming the color material receiving layer was changed to NS625XC made of Takamatsu Oil and Fat and a swollen color material receiving layer was formed.

(Example 31)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that the thickness A of the transparent sheet was changed from 5 μm to 15 μm and the thickness of the colorant receiving layer was changed from 10 μm to 5 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 3.

(Example 32)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that the thickness A of the transparent sheet was changed from 5 μm to 1 μm and the thickness of the colorant receiving layer was changed from 10 μm to 15 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.07.

(Example 33)
A transfer material and a recorded material were obtained in the same manner as in Example 29 except that the thickness A of the transparent sheet was changed from 5 μm to 20 μm and the thickness B of the colorant receiving layer was changed from 10 μm to 5 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 4.0.

(Example 34)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that the thickness A of the transparent sheet was changed from 5 μm to 0.5 μm and the colorant receiving layer was changed from 10 μm to 15 μm. The ratio (A / B) between the thickness A of the colorant receiving layer and the thickness B of the transparent sheet was 0.03.

(Example 35)
[Preparation of aqueous polyethylene glycol solution]
Polyethylene glycol (PEG, polymerization degree 1000) was dissolved in ion-exchanged water to prepare a polyethylene glycol aqueous solution having a solid content of 8%.

[Manufacture of transfer material]
A transfer material and recorded matter were obtained in the same manner as in Example 29, except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of PVA aqueous solution was changed to 0.5 part of polyethylene glycol (PEG) aqueous solution. It was.

(Example 36)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution was changed to 0.1 part of the aqueous polyethylene glycol solution. The content of the swellable resin is shown in Table 6.

(Example 37)
A transfer material and recorded matter were obtained in the same manner as in Example 29, except that in the preparation of the coating liquid for forming the transparent sheet, 1 part of PVA aqueous solution was changed to 0.5 part. The content of the swellable resin in the transparent sheet is shown in Table 6.

(Example 38)
A transfer material and recorded matter were obtained in the same manner as in Example 29 except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution was changed to 0.1 part. The content of the swellable resin in the transparent sheet is shown in Table 6.

(Example 39)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution was changed to 0.3 part. The content of the swellable resin in the transparent sheet is shown in Table 6.

(Example 40)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that the PVA aqueous solution 1, 0.5 part was changed to 3 parts in the preparation of the coating liquid for forming the transparent sheet. The content of the swellable resin in the transparent sheet is shown in Table 6.

(Example 41)
A transfer material and recorded matter were obtained in the same manner as in Example 29, except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution was changed to 0.01 part. The content of the swellable resin in the transparent sheet is shown in Table 6.

(Example 42)
A transfer material and recorded matter were obtained in the same manner as in Example 29, except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution 1 was changed to 0.5 part of the PVA aqueous solution 2.

(Example 43)
A transfer material and recorded matter were obtained in the same manner as in Example 29, except that in the preparation of the coating liquid for forming the transparent sheet, 0.5 part of the PVA aqueous solution 1 was changed to 0.5 part of the PVA aqueous solution 3.

(Example 44)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that 0.5 part of the PVA aqueous solution 1 was changed to 0.5 part of the PVA aqueous solution 4 in the preparation of the coating liquid for forming the transparent sheet.

(Example 45)
A transfer material and a recorded matter were obtained in the same manner as in Example 29 except that 0.5 part of the PVA aqueous solution 1 was changed to 0.5 part of the PVA aqueous solution 5 in the preparation of the coating liquid for forming the transparent sheet.

(Example 46)
[Manufacture of transfer material]
Transfer in the same manner as in Example 29 except that 0.5 part of the PVA aqueous solution 1 was changed to 1 part of the NS625XC aqueous solution made of Takamatsu Yushi (solid content concentration 8%) in the preparation of the coating liquid for forming the transparent sheet. Materials and recorded materials were obtained.

  The following evaluation was performed on the above examples.

[Evaluation <Crack of Transparent Sheet>]
The recorded material was immersed in tap water for 48 hours and taken out from the water, and then the surface was lightly wiped, and then the cracks of the transparent sheet were observed visually and with a microscope.
A: There is no crack.
○: Although there is no crack, small wrinkle marks can be confirmed.
(Triangle | delta): Although there is no crack, a big wrinkle trace can be confirmed.
X: Wrinkle marks remain and a large amount of cracks can be confirmed visually.

[Evaluation <Transfer / Peelability>]
Using the transfer material of Example or Comparative Example, a color material receiving layer was transferred to an image support to produce a recorded material, and the degree of transfer of the color material receiving layer and peeling of the base material sheet at that time was evaluated. . Evaluation was performed visually. The results are shown in Tables 3, 4, and 5 below.
◯: The colorant receiving layer is well transferred to the image support, and the base sheet is also peeled off well. There is no peeling of the transparent sheet.
Δ: There is a portion where the colorant receiving layer is not transferred to the image support, or partial peeling of the transparent sheet is observed. Alternatively, there is a portion where the base sheet does not peel.
X: The colorant receiving layer and the transparent sheet are not transferred to the image support.

[Evaluation <Contaminated Water>]
One drop of dye ink having a colorant concentration of 5% was dropped on the transparent sheet, and after 30 seconds of dropping, the dye ink was wiped off, and the dyeing condition of the transparent sheet was visually observed.
○: Dyeing is not seen on the transparent sheet.
Δ: A part of the transparent sheet is dyed, but the recording information of the colorant receiving layer can be recognized.
X: The transparent sheet and the color material receiving layer are dyed, and the recorded information of the color material receiving layer is unrecognizable.

1 Transfer material 50 Base sheet 52 Transparent sheet (protective sheet)
52A pore 53 color material receiving layer 55 image support 72 image 73 recorded matter 650 spur 657 needle 658 laser processing apparatus

Claims (10)

A base material sheet, a protective sheet, and a color material receiving layer are transfer materials laminated in this order,
The colorant receiving layer contains a water-soluble resin,
The protective sheet contains polyvinyl alcohol having an average degree of polymerization of 1,500 to 5,000 ,
Content of the said polyvinyl alcohol is 0.05 mass% or more and 2.0 mass% or less, The transfer material characterized by the above-mentioned.   The transfer material according to claim 1, wherein the degree of saponification of the polyvinyl alcohol is 86 mol% or more. The transfer material according to claim 1, wherein the moisture permeability of the protective sheet is 5 g / m ² · h or more. The ratio (A / B) between the thickness A of the protective sheet and the thickness B of the colorant receiving layer is in the range of the formula (1), according to any one of claims 1 to 3. The transfer material described.
0.07 ≦ (A / B) ≦ 3.00 (1)   The transfer material according to any one of claims 1 to 4, wherein the protective sheet is formed mainly of an acrylic and / or urethane resin. The base sheet, transfer material according to any one of claims 1 5, characterized in that the peelable. An image support, a colorant receiving layer on which an image is recorded, and a protective sheet are sequentially stacked recordings,
The colorant receiving layer contains a water-soluble resin,
The protective sheet contains polyvinyl alcohol having an average degree of polymerization of 1,500 to 5,000 ,
Content of the said polyvinyl alcohol is 0.05 mass% or more and 2.0 mass% or less, The recorded matter characterized by the above-mentioned.   The recorded matter according to claim 7, wherein the degree of saponification of the polyvinyl alcohol is 86 mol% or more.   The recorded matter according to claim 7 or 8, wherein the protective sheet is formed mainly of an acrylic and / or urethane resin. An image support, a colorant receiving layer on which an image is recorded, and a protective sheet are a method for producing a recorded matter in which layers are sequentially laminated,
Step 1 of recording an image by ink jet recording on the colorant receiving layer of the transfer material according to any one of claims 1 to 6 ,
Step 2 of heat-pressing the colorant receiving layer of the transfer material to the image support;
And a step 3 of peeling the base sheet from the transfer material.