JP2009297930A - Intermediate transfer recording medium and image recording fiber base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate transfer recording medium and an image recording fiber base material which enables printing an image by ink jet printing, causes no image blur, dries quickly, and causes the transferred image onto the media to be superior in scratch resistance and durability such as fastness to washing. <P>SOLUTION: The intermediate transfer recording medium 10 consists of a laminate of a base material 11, a demolding layer 13, and a protection layer 15, and a receiving layer 21, the protection layer 15 including a cross-linking polyester resin and a filler, the receiving layer 21 characteristically including a cation urethane resin, a cation fixing agent, an aziridine derivative whose filler and molecule have two or more aziridinyl groups therein, the ratio of the cross-linking polyester resin to the filler in the protection layer 15 characteristically being 100:5 to 100:20, the ratio of the caotin urethane resin to the aziridine derivative whose molecule have two or more aziridinyl groups in the receiving layer 21 being characteristically 100:1 to 100:15. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an intermediate transfer recording medium, and more specifically, it is possible to easily print a desired image of only one sheet or a small lot for personal use by an inkjet method, and overlay the image on a fibrous material such as a T-shirt. The image can be easily transferred by heating and pressing with an iron or the like, and the image after transfer relates to an intermediate transfer recording medium excellent in durability such as scratch resistance and fastness to washing, and an image recording fiber base material.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. “PET” is an abbreviation, functional expression, common name, or industry term for “polyethylene terephthalate” and “MEK” for “methyl ethyl ketone”.

  (Main application) The main application of the image recording fibrous base material (transfer object, medium) obtained by transferring an image using the intermediate transfer recording medium of the present invention is composed of, for example, a fibrous base material. Clothing such as T-shirts, cartons, cases, packaging materials such as exterior paper, accessories such as bags, appreciation tickets, greeting cards, envelopes, tags, bookmarks, calendars, posters, brochures, nameplates, report paper, etc. There are stationery, building materials, panels, emblems, footwear and shoes. However, it is not particularly limited as long as it is an application for transferring only one sheet or a small lot image for personal use by heating and pressing with an iron or the like.

(Background Art) In recent years, personal preferences have been diversified and personalized, and many personal products have a tendency to produce a variety of small lots. For stationery and apparel products, there is a demand for only one product per person. However, conventional image formation on textile materials such as cloth and paper, such as T-shirts, can be directly screen-printed or transferred to T-shirts after printing on transfer paper by offset or screen printing methods. However, a small lot product has a problem that the manufacturing cost is extremely increased, which is not realistic.
Therefore, a small lot image forming method on fabric materials such as cloth and paper can be easily manufactured at low cost, and the image quality is high, and the durability in use such as washing is excellent. Is required.

(Prior art) Conventionally, the pattern holding layer is composed of a hydrophilic polymer, and the pattern holding layer is made of a hydrophilic polymer, and the ink absorption of the pattern holding layer is an adhesive layer. A transfer sheet (corresponding to the intermediate transfer recording medium of the present invention) is known in which a pattern is formed by allowing ink to permeate from the adhesive layer side by making it greater than the ink absorbency of For example, see Patent Document 1.) However, there is a problem that the material is limited to make a difference in ink absorbability between the pattern holding layer and the adhesive layer, and the manufacturing cost is high.
In addition, a thermal transfer sheet that is transferred by pressing on the surface of a T-shirt or the like with a heated iron, a silicone layer is formed on one side so that the color toner image of the transfer sheet transferred to the T-shirt or the like does not surface. A layer formed with a dry coating film in which a solvent-based polyurethane resin is applied to a substrate, 15 parts of titanium oxide, 50 parts of porous silica mixed product, thermoplastic powder, etc. on a water-soluble polyurethane resin on the a layer. A layer b formed with a mixed urethane resin water-based ink receiving layer as a dry coating film, and a dry coating film obtained by applying a porous silica-mixed product and a urethane resin mixed with thermoplastic powder on the layer b. A water-repellent thermal transfer sheet composed of the formed c layer is known (for example, see Patent Document 2). However, the receiving layer is composed of three layers of a layer, b layer, and c layer, and there is a disadvantage that the process is complicated and the cost is high.
Further, the present applicant also forms the receptor layer on the transfer object by thermal transfer, and the receptor layer has a porous or particulate form for receiving the ink for ink jet. An ink-jet receiving layer transfer sheet (corresponding to the intermediate transfer recording medium of the present invention) in which a releasable receiving layer is provided on one surface of a base material capable of obtaining high image quality regardless of the above is disclosed. (For example, refer to Patent Document 3). However, the purpose is to obtain a high image quality equivalent to that of special paper, and there is no description or suggestion about durability in use such as washing of images.

JP-A-62-242600 JP 2004-232148 A JP 11-277895 A

  Accordingly, the present invention has been made to solve such problems. The purpose is to form an image on a fibrous material such as a small lot of cloth or paper, and it is possible to print only one sheet for personal use or a favorite image of a small lot easily and at low cost by the inkjet method. Can be easily transferred by heating and pressing with an iron or the like on a fibrous material such as a T-shirt, and the transferred image is an intermediate transfer recording medium excellent in durability such as scratch resistance and fastness to washing, and image recording. It is to provide a fibrous base material.

In order to solve the above problems, an intermediate transfer recording medium according to the invention of claim 1 is an intermediate formed by laminating a base material and at least a release layer, a protective layer and a receiving layer on one surface of the base material. A transfer recording medium, wherein the protective layer includes a crosslinked polyester resin obtained by crosslinking a saturated copolymerized polyester resin with an isocyanate compound and a filler, and the receiving layer includes a cationic urethane resin, a cationic fixing agent, a filler, and an intramolecular And an aziridine derivative having two or more aziridinyl groups, and the receiving layer can be printed by an ink jet method.
In the intermediate transfer recording medium according to the second aspect of the present invention, the proportion of the filler in the protective layer relative to the crosslinked polyester resin is based on mass, the crosslinked polyester resin: filler = 100: 5 to 20, and the cation of the receiving layer. The proportion of the aziridine derivative having two or more aziridinyl groups in the molecule relative to the functional urethane resin is based on mass, and the cationic urethane resin: the aziridine derivative having two or more aziridinyl groups in the molecule = 100: 1 to 15 so that it is.
The image-recording fibrous base material according to the invention of claim 3 is provided with a fibrous base material and a fixing layer containing a saturated copolymerized polyester resin on one surface of the fibrous base material, An image is printed on the receiving layer of the intermediate transfer recording medium according to any one of 1 and 2 by an inkjet method, and then the protective layer and the receiving layer on which the image is formed are transferred. .

According to the first aspect of the present invention, an image can be formed on a fibrous material such as a small lot of cloth or paper by using an ink jet method for a single image for personal use or a small lot of preferred images at low cost. The image can be printed easily, and the image can be easily transferred by overlaying it on a fibrous material such as a T-shirt and heated and pressed with an iron, etc., and the transferred image is an intermediate transfer excellent in durability such as scratch resistance and fastness to washing. A recording medium is provided.
According to the second aspect of the present invention, in addition to the effect of the first aspect, an intermediate transfer recording medium that is more excellent in durability such as scratch resistance and fastness to washing is provided.
According to the third aspect of the present invention, an image recording fibrous base material excellent in durability, such as scratch resistance and fastness to washing, can be provided. The

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of an intermediate transfer recording medium showing one embodiment of the present invention.
FIG. 2 is a cross-sectional view in which an image is formed on the intermediate transfer recording medium of the present invention.
FIG. 3 is a cross-sectional view illustrating iron transfer between the intermediate transfer recording medium of the present invention on which an image has been formed and a fibrous base material provided with a fixing layer.
FIG. 4 is a cross-sectional view of an image recording fibrous base material showing one embodiment of the present invention.
FIG. 5 is a process diagram illustrating a process of transferring to a fibrous base material using the intermediate transfer recording medium of the present invention.

  (Intermediate transfer recording medium) As shown in FIG. 1, the intermediate transfer recording medium 10 of the present invention has a base material 11, a release layer 13, a protective layer 15, and a receiving layer 21 on one surface of the base material 11. Have You may provide other layers, such as a primer layer and a printing layer, in these interlayers and / or the layer surface as needed. The protective layer 15 includes a crosslinked polyester resin obtained by crosslinking a saturated copolymerized polyester resin with an isocyanate compound and a filler. Preferably, the blending ratio of the filler to the crosslinked polyester resin is based on mass, and the crosslinked polyester resin: filler = 100: 5 to 20 And The receiving layer 21 contains a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, and can be printed on the receiving layer 21 by an ink jet method. Is based on the mass ratio of the aziridine derivative having two or more aziridinyl groups in the molecule with respect to the cationic urethane resin of the receptor layer 21, and the cationic urethane resin: having two or more aziridinyl groups in the molecule. Aziridine derivative = 100: 1 to 15. Further, FIG. 2 shows a state in which the image 103 is printed on the receiving layer 21 by the ink jet method. The intermediate transfer recording medium 10 of the present invention on which the image 103 is printed is transferred to the transfer target (fibrous base material 101) as shown in FIG. 3, so that the image recording fibrous base material 100 as shown in FIG. It becomes.

  The intermediate transfer recording medium 10 can achieve the following effects. (1) The protective layer 15 includes a cross-linked polyester resin obtained by cross-linking a saturated copolyester resin with an isocyanate compound and a filler, so that the wear resistance and scratch resistance (scratch resistance) durability are comparable to those of an ultraviolet curable resin. Excellent. (2) Since the protective layer 15 is not an ultraviolet curable resin, it does not irradiate ultraviolet rays, does not require this step, and does not require an ultraviolet irradiation device, and can be easily manufactured by a conventional device. (3) When the protective layer 15 and the receiving layer 21 are transferred from the intermediate transfer recording medium 10 to the fibrous base material 101 which is a transfer target, the protective layer 15 is easily peeled off from the release layer 13. Even a household iron can be transferred with good transferability. (4) The receiving layer 23 contains a cationic urethane-based resin, a cationic fixing agent, and a filler, and can print an image such as personal information with an ink-jet method with good drying properties. (5) In addition, the receiving layer 23 also contains an aziridine derivative having two or more aziridinyl groups in the molecule, so that the ink-fixing property of the ink jet system is good, and durability such as solvent resistance and washing resistance is improved. Excellent.

  The image recording fibrous base material 100 can exhibit the following effects. (1) The protective layer 15 and the receiving layer 21 (the image 103 is printed) are transferred to the image recording fibrous base material 100, and the outermost surface of the image recording fibrous base material 100 becomes the protective layer 15, and the protection The layer 15 includes a crosslinked polyester resin obtained by crosslinking a saturated copolymerized polyester resin with an isocyanate compound and a filler, and has excellent wear resistance and scratch resistance (scratch resistance) durability comparable to an ultraviolet curable resin. (2) Therefore, it is excellent in wear resistance, scratch resistance (scratch resistance) durability even after repeated use, and compared with a protective layer made of a conventional UV curable resin (also called a hard coat layer). However, the surface of the medium can be strongly protected without inferiority. (3) Since the image 103 printed on the receiving layer 23 is an ink-jet printing, the image does not use an ink ribbon, unlike a transfer image obtained by a thermal transfer method using a melt transfer or sublimation type thermal transfer ink ribbon. Therefore, there is no trace of personal information and the security is excellent. (4) Further, since the image 103 is an ink-jet printing, it is possible to print only one sheet or a small lot of favorite images for personal use at a low cost. (5) Since the image 103 can be easily transferred by superimposing it on a fibrous base material such as a T-shirt and heating and pressing with an iron or the like, a desired image can be formed on only one sheet for personal use. Can do. (6) The receiving layer 21 on which the transferred image 103 is printed is sandwiched between the protective layer 15 and the fixing layer 31, and is resistant to friction and scratching due to external force, and is also resistant to fading even during washing. Excellent.

  (Substrate) The substrate 11 is not particularly limited. Specific examples of the preferred substrate 11 include polyester, polypropylene, polycarbonate, cellulose acetate, and polyethylene derivatives having high heat resistance such as polyethylene terephthalate and polyethylene naphthalate. And stretched or unstretched films of plastics such as polyamide and polymethylpentene. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. Although the thickness of a base film can be suitably selected according to material so that the intensity | strength, heat resistance, etc. may become appropriate, the thing about 1-100 micrometers is normally used normally.

  (Release layer) A release layer 13 may be provided to improve the releasability during transfer, and a release layer may be provided instead of the release layer 13 as necessary. If both are provided, the transferability can be further improved.

(Release layer) As the release layer 13, there are usually a release resin, a resin containing a release agent, a curable resin which is cross-linked by ionizing radiation, etc., preferably a melamine-based resin, which will be described later. By combining with the hard coat layer 14, the releasability from the release layer 13 is stabilized, and the transferability during transfer can be improved. The release layer 13 is formed by dispersing or dissolving the resin in a solvent, applying and drying the resin by a known coating method such as roll coating or gravure coating, and baking at a temperature of about 150 ° C to 200 ° C. The thickness of the release layer 13 is usually about 0.01 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.
(Peeling layer) As a peeling layer provided as needed, generally cellulose derivatives such as ethyl cellulose, nitrocellulose, cellulose acetate, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, It is formed using thermoplastic resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, etc., and thermosetting resins such as unsaturated polyester resin, polyurethane resin, and amino alkyd resin. be able to. The release layer preferably contains a filler such as microsilica or polyethylene wax in order to improve the foil breakability. The release layer may be prepared by dispersing or dissolving the above resin in a solvent and applying at least one part by a known coating method such as roll coating, gravure coating, bar coating, etc. and drying to form a coating film. good. The thickness of the release layer is usually about 0.1 μm to 5 μm, preferably about 0.5 μm to 2 μm. When both the release layer 13 and the release layer are provided, they may be used in combination as appropriate. In this case, the release layer is transferred to the transfer target after transfer, and has a function as a protective layer. .

  (Protective layer) The protective layer 15 includes a crosslinked polyester resin obtained by crosslinking a saturated copolymer polyester resin with an isocyanate compound and a filler. The saturated copolyester resin has a hydroxyl group at the terminal, and examples thereof include commercially available Elitel UE3410 and UE-3510 manufactured by Unitika. Examples of the isocyanate compound include isocyanate compounds containing two or more isocyanate groups and urethane resins, such as commercially available Coronate L and Coronate HL from Nippon Polyurethane, Takenate D103H and Takenate D165N from Mitsui Polyurethane. What is necessary is just to bridge | crosslink said saturated copolyester resin with said isocyanate compound as a crosslinked polyester resin.

  (Formation of Protective Layer) The protective layer 15 is a well-known roll coat, gravure coat, comma coat, etc. by dispersing or dissolving a saturated copolymerized polyester resin, an isocyanate compound, a filler and, if necessary, an additive in a solvent. After coating and drying, the protective layer 15 is cured (reacted) in a greenhouse. The thickness of the protective layer 15 is usually about 1 μm to 30 μm, preferably about 2 μm to 20 μm. It may be applied several times.

  Examples of the filler include micro silica and polyethylene wax. Preferably, the blending ratio of the filler to the crosslinked polyester resin is based on mass, and the crosslinked polyester resin: filler = 100: 5 to 20. Below this range, the scratch resistance is insufficient, and beyond this range, the transparency is lowered.

  (Receiving layer) The receiving layer 21 is provided on the surface of the protective layer 15 through a primer layer as necessary. The receiving layer 21 becomes the outermost surface of the intermediate transfer recording medium 10, and an image is printed on the receiving layer 21 by an ink jet method. The inkjet receiving layer 21 is obtained by applying an inkjet receiving layer composition. The inkjet receiving layer composition includes at least a cationic urethane-based resin, a cationic fixing agent, a filler, and two or more aziridinyl in a molecule. And an aziridine derivative having a group. Among the components of the receiving layer 21, it is assumed that a plurality of components are reacting with each other, but the product is not clear, and the receiving layer 21 of the present invention includes a reaction product between components.

  Polycationic polyurethane resins with cationic groups, polytetramethylene ether glycol polyurethane, polyester ether polyurethane, polybutylene adipate polyurethane, polymethylpentane adipate polyurethane, polynonanediol adipate / polyoctane adipate Polyurethane resins such as polyurethane and polymethylpentane adipate polyurethane, preferably self-emulsifying or aqueous, and a reaction product of a polycarbonate or polyester polyol having a cationic hydrophilic group and an aliphatic isocyanate compound. Examples of cationic groups include primary to tertiary amines or quaternary ammonium bases.

  (Cationic Fixing Agent) Examples of the cationic fixing agent include dye fixing agents such as polyamine derivatives and quaternary ammonium salts.

  (Filler) As the filler, micro-silica is preferable because it contains fine particles such as silica, alumina, calcium carbonate, and plastic pigment, wax, and the like so as to improve foil cutting properties and not to impair transparency.

（式中、Ｒ₁は水素原子、炭素数１〜３のアルキル基、又はＲ₂−ＯＣＨ₂−で、Ｒ₂〜₅は水素原子、塩素原子、アルキル基、ハロゲン化アルキル基、アルキルアルコール基、アクリル酸アルキル基、アルキルフェノール基で、同一でも異なってもよい。）

（式中、Ｒ₆〜₁₀は水素原子、塩素原子、アルキル基、ハロゲン化アルキル基、アルキルアルコール基、アクリル酸アルキル基、アルキルフェノール基で、同一でも異なってもよい。ｎは１〜３の整数）
一般式１におけるＲ₃〜₅のうち２個以上が一般式２の構造を有する化合物、即ち、分子内に２個以上のアジリジニル基を有するアジリジル誘導体である。 (Aziridinine derivative) As the aziridyl derivative, a compound having two or more aziridinyl groups in the molecule is used.

(In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or R ₂ —OCH ₂ —, and R ₂ to ₅ are a hydrogen atom, a chlorine atom, an alkyl group, a halogenated alkyl group, or an alkyl alcohol group. An alkyl acrylate group or an alkylphenol group, which may be the same or different.)

(Wherein R ₆ to ₁₀ are a hydrogen atom, a chlorine atom, an alkyl group, a halogenated alkyl group, an alkyl alcohol group, an alkyl acrylate group or an alkylphenol group, and may be the same or different. N is an integer of 1 to 3) )
Two or more of R ₃ to ₅ in the general formula 1 are compounds having the structure of the general formula 2, that is, aziridyl derivatives having two or more aziridinyl groups in the molecule.

  Aziridine derivatives having two or more aziridinyl groups in the molecule, such as trimethylolpropane-tris- (α-methyl-α-aziridinyl acetate), trimethylolpropane-tris- (α-ethyl-α-aziridinini) Acetate), trimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (1-aziridinylpropionate)), trimethylolbutane- Tris- (β- (1-aziridinylpropionate)), monoethoxytrimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- ( 2-methyl-1-aziridinylpropionate)), tetramethylolmethane-tris- (α-methyl-α-aziridinyl a) Tate), tetramethylolethane-tris- (β- (1-aziridinylpropionate)), ditrimethylolpropane-hexakis- (β-aziridinylpropionate), ditrimethylolpropane-pentakis- (β- (2-methylaziridinyl propionate) and the like.

  Preferably, trimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (1-aziridinylpropionate)), trimethylolpropane-tris -(Β- (1-aziridinylpropionate)), trimethylolbutane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (2-methyl -1-aziridinylpropionate)), trimethylolpropane-tris- (β- (2-methyl-1-aziridinylpropionate)), trimethylolpropane-tris- (β- (2,2 -Dimethyl-1-aziridinylpropionate)), trimethylolpropane-tris- (α-methyl-β- (1-aziridinylpropionate), trimethylo Propane-tris- (β-methyl-β- (1-aziridinylpropionate), tetramethylolmethane-tris- (α-methyl-α-aziridinyl acetate), tetramethylolmethane-tris- (β- (1-aziridinylpropionate), tetramethylolethane-tris- (β- (1-aziridinylpropionate)), tetramethylolmethane-tris- (β- (2-propyl-1-aziridini) Lupropionate)), tetramethylolmethane-tris- (β- (2-methyl-1-aziridinylpropionate)), tetramethylolmethane-tris- (β- (2,2-dimethyl-1-) Aziridinylpropionate), tetramethylolmethane-tris- (β- (2,2-diethyl-1-aziridinylpropionate) tetramethylo Rumethane-tetrakis-β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis-β-methyl-β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis-β- (2 -Methyl-1-aziridinylpropionate), ditrimethylolpropane-hexakis- (β-aziridinylpropionate), ditrimethylolpropane-pentakis- (β- (2-methylaziridinylpropionate) Are preferred, trimethylolpropane-tris- (β- (1-aziridinylpropionate), tetramethylolmethane-tris- (β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis- ( β-aziridinylpropionate).

  Examples of commercially available aziridine derivatives having two or more aziridinyl groups in the molecule include TAZM (trimethylolpropane-tris- (β-aziridinylpropionate), TAZO, manufactured by Mutual Yakuhin Co., Ltd.). (Tetramethylolmethane-tris- (β- (1-aziridinylpropionate))) Nippon Shokubai Chemite PZ-33 (trimethylolpropane-tris- (β-aziridinylpropionate)) and the like An aziridine derivative having three aziridinyl groups is particularly preferable because of its high reactivity and a high network durability after curing.

  The ratio of cationic urethane resin, cationic fixing agent, microsilica, and aziridine derivative having two or more aziridinyl groups in the molecule is based on mass. Cationic urethane resin: cationic fixing agent: microsilica: intramolecular The aziridine derivative having two or more aziridinyl groups in the group is 100: 5 to 20: 1 to 10: 1 to 15. If the content of the cationic fixing agent is less than the above range, the fixing property is poor, and if it exceeds the above range, it elutes during washing and lowers the fastness. If the content ratio of the microsilica is less than the above range, the ink fixing property is poor, and if it exceeds the above range, the transparency is lowered and the image becomes difficult to see.

  The addition amount of the aziridine derivative is not particularly limited as long as it does not inhibit the effect of the present invention, but the blending ratio of the aziridine derivative having two or more aziridinyl groups in the molecule with respect to the cationic urethane resin is usually on a mass basis. Cationic urethane resin: Aziridine derivative having two or more aziridinyl groups in the molecule = 100: 1 to 15 is preferable, and 100: 3 to 10 is more preferable. Since the aziridine derivative functions as a water-soluble curing agent, if the content ratio of the aziridine derivative is less than the above range, since the curing is insufficient, durability such as water resistance and alcohol resistance is not sufficient, If it exceeds the above range, the transparency is lowered and the image becomes difficult to see.

  The receiving layer 21 for inkjet is formed by dispersing or dissolving the above materials in a solvent, adding an additive as necessary, and applying corona treatment or a primer layer to at least one surface of the medium 101 as necessary. May be applied and dried by a known coating method such as roll coating, gravure coating, comma coating or die coating. The thickness thereof is usually about 1 μm to 15 μm, preferably about 2 μm to 10 μm.

  (Other layers) The layers provided on the interlayer and / or the layer surface as needed include a primer layer, a printing layer, an antistatic layer, a back-sliding layer, etc., and each may be a known layer. In particular, the printing layer may be printed by a known screen printing or gravure printing method using colored ink or fluorescent ink.

  (Primer layer) In particular, when the receptor layer 21 is provided, it is preferable to provide a primer layer on the surface of the protective layer 15 in order to improve the adhesive force. Examples of the primer layer include polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acid Modified polyolefin resins, copolymers of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl acetal resins, polybutadiene resins, rubber compounds, etc. can be used. Preferably, those having oxygen or nitrogen, or those having a reactive isocyanate compound, such as those known as conventional adhesives such as acrylic resins, urethane resins, amide resins, epoxy resins, ionomer resins, rubber resins, etc. is there. The primer layer is not necessarily contained since it has a thin film thickness, but it is preferable to contain a filler such as microsilica or polyethylene wax.

  (Fibrous base material) The fibrous base material 101 to be transferred (medium) is not particularly limited as long as it is fibrous. For example, fibers such as cloth, plant pulp, plastic, glass, metal, ceramics, etc. Any of woven fabrics, non-woven fabrics, paper-made ones, and the like may be used. Further, at least a part of the medium of the fibrous base material 101 may be colored, printed, or otherwise decorated.

  As shown in FIG. 5, in the transfer method to the fibrous base material 101, the intermediate transfer recording medium 10 is prepared in step S11, and an image is formed on the surface of the receiving layer 21 of the intermediate transfer recording medium 10 in step S12. Separately, the fibrous base material 101 is prepared in step S21, and the fixing layer 31 is formed on the transfer surface of the fibrous base material 101 in step S22. Next, in step S33, the surface of the receiving layer 21 on which the image of the intermediate transfer recording medium 10 is formed in step S12 and the surface of the fixing layer 31 of the fibrous base material 101 on which the fixing layer 31 is formed in step S22 are overlapped. In addition, as shown in FIG. 3, the image recording fiber base material 100 is obtained by transferring by heating and pressing with an iron or the like, and peeling and removing the base material 11 and the release layer 13 in step S <b> 34. .

  (Fixing layer) The fixing layer 31 is not particularly limited as long as it is softened and / or melted by heat and pressure at the time of transfer with the binder contained in the receiving layer and is closely integrated. For example, polyester resins, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, modified resins of these resins, and these resins Preferably, it is a polyurethane-based resin that is the same resin as the binder resin of the receiving layer 21, a polyester-based resin, more preferably a saturated copolymerized polyester resin, and the saturated copolymerized polyester resin has a hydroxyl group at the terminal. Examples include commercially available Elitel UE3410, UE-3510, etc. manufactured by Unitika.

  (Formation of Fixing Layer) The fixing layer 31 is a known coating method such as roll coating, brush coating, ink jet coating, spray coating, etc. by dispersing or dissolving a polyester resin and, if necessary, additives in a solvent. Apply and dry. The thickness of the fixing layer 31 is usually about 5 μm to 100 μm, preferably about 10 μm to 50 μm. It may be applied several times. A spray coat in which the application location can be freely selected is preferable.

  In the receiving layer 21 of the intermediate transfer recording medium 10 of the present invention, the binder contained in the transfer layer has thermal adhesiveness, and is closely integrated by heat during transfer, so that the transfer can be performed and the transferred object can be transferred. Since the fixing layer 31 is provided in order to increase the adhesion function when transferring to the fibrous base material 101, which is a body, the receiving layer 21 is softened and softened by heating and pressurization during transfer onto the surface of the fibrous base material 101. It is possible to perform transfer that melts and / or adheres firmly.

  (Inkjet) The formation of the image 103 on the surface of the receptor layer 21 of the intermediate transfer recording medium 10 in step S12 may be performed by printing on the receptor layer 21 by an inkjet method. The ink jet method includes an impact method using heat and pressure, but is not particularly limited. The ink jet ink includes water-based and oil-based inks, but is not particularly limited. Also, the image 103 formed by the ink jet method may be a spot shape such as a circle or a star, or any shape such as letters, numbers, illustrations, and photographs, and the color tone is not limited to a single color, a plurality of colors, or a full color image. Absent. Preferably, variable information can be printed on demand by an ink jet method, or only one image can be printed for personal use. Moreover, printing can be performed easily and at low cost. In addition, in the inkjet method, an ink ribbon that leaves traces of personal information or the like is not used when the image 103 is printed. Also, when the image 103 is printed, since the image does not blur and dries quickly, it is efficient. Can be printed.

  (Transfer) As shown in FIG. 3, the transfer process to the fibrous base material 101 transfers the receiving layer 21 surface of the intermediate transfer recording medium 10 on which the image 103 is formed to the fixing layer 31 surface of the fibrous base material 101 surface. Superimpose and heat to peel off and transfer the substrate. The receiving layer 21 formed with the image 103 / primer layer (if necessary) / protective layer 15 is transferred to the fibrous base material 101 to form the image recording fibrous base material 100. The transfer method may be a known transfer method, for example, hot stamping by hot stamping (foil stamping), whole surface or stripe transfer by a thermal roll, thermal printer (also called thermal transfer printer) by a thermal head (thermal printing head), etc. The known method can be applied, and can be easily transferred by hand as shown in the drawing. The shape of the transfer may be an arbitrary shape such as a spot shape such as a circle, a rectangle, or a star.

  (Inline operation) The printing and transfer of the image 103 may be separate offline operations or continuous inline operations. Preferably, even in-line operation, the image 103 does not bleed and dries quickly, so that the transfer operation can be performed immediately after the image 103 is printed.

  (Fixability) Although images can be easily formed as images by the conventional ink jet method, these images have a drawback that they are inferior in durability, particularly in friction resistance. Conventional ink-receiving layers are mainly composed of water-soluble resins such as polyvinyl alcohol, and the water resistance is remarkably poor. Also, porous fillers are used, and good and poor solvents are used as the solvent for the receiving layer coating solution. The solvent used a phase separation and gelation during drying to give a porous network structure, but the image fixability was not sufficient, and the image faded or bleeds during washing. There was also a problem.

  On the other hand, the image 103 printed on the receiving layer 21 of the intermediate transfer recording medium of the present invention by the ink jet method has high image quality and good fixability, and the printed image has scratch resistance, water resistance and alcohol resistance. It has excellent durability such as solvent resistance such as washability and fastness to washing. Although coexistence of fixing property and fastness to washing is not certain, by including a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, The surface has fine irregularities, the coating itself is not dense and is rather rough, and an aziridine derivative having two or more aziridinyl groups in the molecule reacts with other components. As a result, the network or aggregation state is stabilized, so that the adhesion with the image components is improved, and in particular, the alcohol resistance can be improved. In addition, it is presumed that a dye constituting an image interacts with or reacts with a cationic urethane resin, a cationic fixing agent, an aziridine derivative having two or more aziridinyl groups in the molecule and curing. In addition, the receiving layer 21 on which the transferred image 103 is printed is sandwiched between the protective layer 15 and the fixing layer 31 and is resistant to fading even during washing, has excellent durability, and is a protective layer that is the outermost surface. Since No. 15 contains a crosslinked polyester resin obtained by crosslinking a saturated copolymerized polyester resin with an isocyanate compound and a filler, it is resistant to friction and scratches due to external force and has excellent durability.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.

Example 1 Using a PET film having a thickness of 20 μm as the base material 11, the following release layer resin composition (coating liquid) was dried on one surface of the base material 11 by a gravure coating method, and then 2 μm. It was applied and dried, and baked at 180 ° C. for 20 seconds to form a release layer 13.
・ <Resin layer resin composition>
TCM01 medium (Dainippon Ink Co., Ltd., melamine resin trade name) 25 parts Solvent (MEK: toluene = 1: 1) 75 parts The following protective layer composition was dried on the surface of the release layer 13 with a gravure reverse coater. After coating and drying at 100 ° C. so as to have a thickness of 5 μm, the protective layer 15 was formed by leaving it to stand for 3 days in an environment of 40 ° C.
・ <Protective layer composition>
Elitel UE-3410
(Unitika Ltd., saturated copolymer polyester resin trade name) 100 parts Coronate HL
(Product name: Isocyanate compound, manufactured by Nippon Polyurethane Co., Ltd.) 5 parts Polyethylene wax (average particle size 3 to 5 μm, spherical) 5 parts Solvent (toluene: methyl ethyl ketone = 1: 1) 400 parts The following primer layer on the surface of the protective layer 15 The composition was coated with a gravure coater so that the coating amount after drying was 0.5 μm, and dried at 100 ° C. to form a primer layer.
・ <Primer layer composition working solution>
Polyester resin 20 parts Microsilica (average particle size 0.5 μm) 1 part Solvent (toluene: methyl ethyl ketone = 1: 1) 80 parts Thickness after drying the following receiving layer composition on the surface of the primer layer 16 with a gravure reverse coater Was applied to a thickness of 4 μm and dried to form a receiving layer 21 to obtain an intermediate transfer recording medium 10 on which no image was formed.
・ <Receptive layer composition>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μm) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai, aziridine) Derivative product name) 3 parts Solvent (water) 300 parts

Example 2 An intermediate transfer recording medium 10 of Example 2 was obtained in the same manner as in Example 1 except that the following protective layer composition and receiving layer composition were used.
・ <Protective layer composition>
Elitel UE-3410
(Unitika, saturated copolymer polyester resin trade name) 1000 parts Coronate HL
(Product name: Isocyanate compound, manufactured by Nippon Polyurethane Co., Ltd.) 5 parts Polyethylene wax (average particle size 3 to 5 μm, spherical) 10 parts Solvent (toluene: methyl ethyl ketone = 1: 1) 400 parts <Receptive layer composition>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 5 parts Solvent (water) 300 parts

Example 3 An intermediate transfer recording medium 10 of Example 3 was obtained in the same manner as in Example 1 except that the following protective layer composition and receiving layer composition were used.
・ <Protective layer composition>
Elitel UE-3410
(Unitika Ltd., saturated copolymer polyester resin trade name) 100 parts Coronate HL
(Product name: Isocyanate compound, manufactured by Nippon Polyurethane Co., Ltd.) 5 parts Polyethylene wax (average particle size 3 to 5 μm, spherical) 15 parts Solvent (toluene: methyl ethyl ketone = 1: 1) 400 parts <Receptive layer composition>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 10 parts Solvent (water) 300 parts

Comparative Example 1 An intermediate transfer recording medium 10 of Comparative Example 1 was obtained in the same manner as in Example 1 except that the following protective layer composition and receiving layer composition were used.
・ <Protective layer composition>
Elitel UE-3410
(Unitika Ltd., saturated copolymerized polyester resin trade name) 100 parts Solvent (toluene: methyl ethyl ketone = 1: 1) 400 parts <Receptive layer composition for inkjet>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Solvent (water) 300 parts

Comparative Example 2 An intermediate transfer recording medium 10 of Comparative Example 2 was obtained in the same manner as in Example 1 except that the following protective layer composition and receiving layer composition were used.
・ <Protective layer composition>
Elitel UE-3410
(Unitika Ltd., saturated copolymer polyester resin trade name) 100 parts Coronate HL
(Product name: Isocyanate compound, manufactured by Nippon Polyurethane Co., Ltd.) 5 parts Polyethylene wax (average particle size 3 to 5 μm, spherical) 25 parts Solvent (toluene: methyl ethyl ketone = 1: 1) 400 parts <Receptive layer composition for inkjet>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 20 parts Solvent (water) 300 parts

  (Examples 4 to 6, Comparative Examples 3 to 4) A known aqueous inkjet ink was applied to the receiving layer 21 of the intermediate transfer recording medium 10 of Examples 1 to 3 and Comparative Examples 1 and 2 with a 600 dpi color inkjet printer. In use, a color face photograph was printed as an image 103 by an on-demand method. Separately, using a cotton T-shirt as the fibrous base material 101, solidify Elitel UE-3410 (Unitika Ltd., product name of saturated copolymer polyester resin) slightly larger than the transfer portion to the transfer portion of the T-shirt. The solution was diluted with a solvent (toluene: methyl ethyl ketone = 1: 1) so as to be 10%, sprayed and dried to form a fixing layer 31 having a thickness after drying of 30 to 50 μm. After the image 103 is superimposed on the surface of the fixing layer 31 and transferred by pressing a heated iron from the surface of the base material 11 of the intermediate transfer recording medium 10, the base material 11 and the release layer 13 are peeled off and gradually removed. Thus, T-shirts (image recording fiber base materials 100 of Examples 4 to 6 and Comparative Examples 3 to 4) to which images were transferred were obtained. In addition, there was no problem in printing by the inkjet method on the receiving layer 21 of the intermediate transfer recording medium 10 of Examples 1 to 3 and Comparative Examples 1 and 2.

(Evaluation) Evaluations were made by washing test, scratch resistance and transparency.
In the washing test, according to JIS L-0217 103 method, washing was carried out by repeating washing at 40 ° C. for 12 minutes, rinsing at 40 ° C. for 2.5 minutes three times and drying. Those that did not show any noticeable change in the image and were practically acceptable were accepted.
Scratch resistance was measured by visually recognizing the degree of scratching after reciprocating steel wool No. 0000 10 times under a load condition of 20 kPa (200 g / cm ² ) with respect to the surface of the protective layer 15. Was not accepted, and it was deemed acceptable.
The transparency was evaluated by visually observing a printed image by an ink jet method, and a marked change in the visibility of the image was not recognized and there was no practical problem.

  (Evaluation results) In Examples 4 to 6, the washing test, scratch resistance and transparency were all acceptable. In Comparative Example 4, the washing test and scratch resistance were acceptable, but the transparency was unacceptable. In Comparative Example 3, the transparency was acceptable, but the washing test and scratch resistance were unacceptable.

1 is a cross-sectional view of an intermediate transfer recording medium showing one embodiment of the present invention. FIG. 3 is a cross-sectional view in which an image is formed on the intermediate transfer recording medium of the present invention. FIG. 3 is a cross-sectional view illustrating iron transfer between an intermediate transfer recording medium of the present invention on which an image is formed and a fibrous base material provided with a fixing layer. It is sectional drawing of the image recording fiber base material which shows one Example of this invention. It is process drawing explaining the process of transferring to a fiber base material using the intermediate transfer recording medium of this invention.

Explanation of symbols

10: Intermediate transfer recording medium 11: Base material 13: Release layer 15: Protective layer 21: Receptive layer 100: Image recording fiber base material 101: Fiber base material 103: Image

Claims (3)

An intermediate transfer recording medium comprising a base material and at least a release layer, a protective layer and a receiving layer laminated on one surface of the base material, wherein the protective layer is obtained by crosslinking a saturated copolymerized polyester resin with an isocyanate compound. A crosslinked polyester resin and a filler, wherein the receptor layer includes a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, and the receptor layer is an inkjet system An intermediate transfer recording medium characterized in that printing can be performed with The blending ratio of the filler to the cross-linked polyester resin in the protective layer is based on mass, the cross-linked polyester resin: filler = 100: 5 to 20, and two or more aziridinyls in the molecule with respect to the cationic urethane resin of the receiving layer The blending ratio of the aziridine derivative having a group is, based on mass, cationic urethane-based resin: aziridine derivative having two or more aziridinyl groups in the molecule = 100: 1 to 15; Intermediate transfer recording medium. A fixing layer containing a saturated copolymerized polyester resin is provided on one surface of the fibrous base material and the fibrous base material, and the intermediate transfer recording medium according to any one of claims 1 and 2 is provided on the fixing layer surface. An image-recording fibrous base material, wherein an image is printed on a receiving layer by an inkjet method, and then the protective layer and the receiving layer on which the image is formed are transferred.

Images