JP2015066775A - Combination of thermal transfer sheet and thermal transfer image-receiving sheet, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a combination of a thermal transfer sheet and a thermal transfer image-receiving sheet, which achieves excellent print density as well as excellent release property and transfer property of a protective layer, and gives a high-quality printed matter with good light fastness.SOLUTION: The combination comprises: a thermal transfer sheet 10 having a dye layer 2 disposed on one surface of a substrate 1 and a back surface layer 3 disposed on the other surface of the substrate; and a thermal transfer image-receiving sheet having a dye-receiving layer disposed on one surface of another substrate. The dye layer of the thermal transfer sheet comprises a dye and a binder resin; and one type of a dye layer is disposed or two or more types of dye layers are disposed in a sequence of frames on one surface of the substrate. At least one type of the dye layer contains nitrocellulose as the binder resin, in a range of 50 mass% or more and 100 mass% or less with respect to the total solid content of the binder resin. The dye-receiving layer of the thermal transfer image-receiving sheet comprises a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.

Description

  The present invention relates to a combination of a thermal transfer sheet and a thermal transfer image receiving sheet, and an image forming method.

  Conventionally, various thermal transfer recording systems are known, and among them, a thermal sublimation transfer system is widely used. In this method, a sublimation dye is used as a coloring material, and the dye in the dye layer of the thermal transfer sheet is thermally transferred to the dye receiving layer of the thermal transfer image receiving sheet to form an image. In this method, during thermal transfer, the amount of heating is adjusted with the thermal head of the printer to transfer a large number of 3 or 4 color dots to the dye receiving layer of the thermal transfer image receiving sheet, and the multicolored color dots are transferred. A full color can be reproduced by sequentially superimposing and gradation printing. The image formed in this way is very clear and excellent in transparency because the color material used is a dye, so it is excellent in halftone reproducibility and coordination, and is a full-color photographic image. It is possible to form a high-quality image comparable to

  The dye layer of the heat-sensitive sublimation thermal transfer sheet holds the sublimation dye contained in the dye layer well in the binder resin during storage of the thermal transfer sheet, and the sublimation dye is released well from the binder resin during thermal transfer. That is, there is a demand for high storage stability and dye transfer efficiency.

  As a binder resin that focuses on storage stability, a butyral or acetal resin is known (see Patent Document 1). A dye layer containing a butyral or acetal resin as a binder resin is excellent in storage stability, but has a problem of low dye transfer efficiency and low printing density. Therefore, when these binder resins are used, (i) the amount of the dye layer applied is increased to increase the content of the sublimable dye contained in the dye layer, or (ii) the dye of the thermal transfer sheet It is necessary to improve the print density by a method such as increasing the mass ratio (D / B ratio) of the sublimable dye / binder resin in the layer.

  However, when the coating amount of the above (i) dye layer is increased, a large amount of sublimation dye that does not move to the thermal transfer image-receiving sheet side remains in the dye layer, which is not preferable in terms of cost. . Also, (ii) when the D / B ratio is increased until a sufficient printing density is achieved, depending on the type of dye, the butyral or acetal binder resin cannot retain the sublimable dye, Storage stability is significantly reduced. When storage stability is reduced, when the thermal transfer sheet is stored in a wound state, the dye layer and the back layer provided on the opposite side of the substrate come into contact with each other, so that the dye layer is sublimated from the back layer. The dye migrates (kick), causing a decrease in sheet transportability and a decrease in the function of the back layer. Further, when the product is rolled back onto a bobbin or the like for further product production, the dye transferred to the back layer is retransferred (backed) to the protective layer, and the obtained image is contaminated. In addition, when stored in a high-temperature and high-humidity environment, the dye deposits on the surface of the dye layer, and during printing, the deposited dye comes into contact with the unprinted portion, resulting in soiling that contaminates the unprinted portion. There are various problems.

Cellulose resins such as cellulose acetate propionate and ethyl cellulose are known as binder resins whose main purpose is to improve dye transfer efficiency. However, these binder resins whose main purpose is to improve dye transfer efficiency are excellent in dye transfer efficiency, but have low storage stability, especially when the coating amount of the dye layer is reduced or the D / B ratio is increased. In such a case, the storage stability is lowered, and the above problem is caused.
In other words, storage stability and dye transfer efficiency are in a trade-off relationship, and if a material with high storage stability is selected, the dye transfer efficiency tends to decrease, while a material with high dye transfer efficiency is selected. In such a case, the storage stability tends to decrease. Therefore, a binder resin that satisfies both storage stability and dye transfer efficiency has been desired.

JP 2009-286060 A

In recent years, with the increase in the printing speed of thermal transfer printers using the thermal sublimation transfer method, there has been a problem that sufficient print density cannot be obtained even if printing is performed using a conventional thermal transfer sheet and thermal transfer image receiving sheet. It was. Therefore, attempts have been made to improve the thermal transfer sheet and the thermal transfer image receiving sheet in order to obtain a sufficient print density.
The present applicant uses nitrocellulose as the binder component in the dye layer of the thermal transfer sheet, so that the dye transfer efficiency is high, and even when the ratio of the dye to the binder resin is increased in order to improve the printing density, it is preserved. The knowledge that it was excellent in stability was obtained (Japanese Patent Application No. 2012-066691).
However, when nitrocellulose is used as the binder component in the dye layer of the thermal transfer sheet, the releasability of the thermal transfer image-receiving sheet from the dye-receiving layer deteriorates, and the dye layer and the dye-receiving layer cause thermal fusion. In some cases, when the dye layer is peeled off from the dye receiving layer, there are many cases where peeling marks are formed on the printed matter, and there is a problem that the quality of the printed matter is deteriorated due to heat fusion or peeling marks.
Therefore, when image formation is performed by combining a thermal transfer sheet comprising a dye layer containing nitrocellulose as a binder component and a thermal transfer image-receiving sheet, it is necessary to take measures to satisfy the peelability between the dye layer and the dye-receiving layer. There is.
However, when a release agent is added in order to improve the peelability, there is a problem that part or all of the protective layer is not transferred when the protective layer is transferred. Further, the printed matter is required to have good light resistance.

  The present invention has been made in view of the above-mentioned problems, and while being excellent in printing density, heat fusion, peeling marks, etc. are suppressed, protective layer transferability is excellent, light resistance is good, and high-quality printing. It is an object of the present invention to provide a combination of a thermal transfer sheet and a thermal transfer image receiving sheet from which a product can be obtained, and an image forming method for forming an image using the combination of the thermal transfer sheet and the thermal transfer image receiving sheet.

The combination of the thermal transfer sheet and the thermal transfer image-receiving sheet according to the present invention comprises a thermal transfer sheet in which a dye layer is provided on one side of the substrate and a back layer is provided on the other side of the substrate, and another substrate In combination with a thermal transfer image-receiving sheet provided with a dye-receiving layer on one side thereof,
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The dye-receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.

The image forming method according to the present invention includes a thermal transfer sheet in which a dye layer is provided on one surface of a substrate and a back layer is provided on the other surface of the substrate, and a dye on one surface of the other substrate. An image forming method for forming an image on the thermal transfer image receiving sheet using in combination with a thermal transfer image receiving sheet provided with a receiving layer,
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The dye-receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.

  In the combination of the thermal transfer sheet and the thermal transfer image-receiving sheet and the image forming method according to the present invention, the amino-modified silicone oil in the dye-receiving layer is an amino-modified silicone oil having a diamine in the side chain. It is preferable from the viewpoint that the moldability is further improved and the effect of preventing heat fusion, peeling marks and the like is enhanced.

  In the combination of the thermal transfer sheet and the thermal transfer image receiving sheet and the image forming method according to the present invention, the amino-modified silicone oil in the dye receiving layer is 0.5% by mass or more based on the total solid content of the dye receiving layer. It is preferable that 4 mass% or less is contained. If it is less than 0.5% by mass, the amount of the release agent in the layer is insufficient, and there is a possibility of inducing heat fusion or peeling marks. On the other hand, if it exceeds 4% by mass, the transferability of the protective layer may be adversely affected.

  According to the combination of the thermal transfer sheet and the thermal transfer image-receiving sheet of the present invention and the image forming method using this combination, thermal fusion, peeling marks and the like are suppressed while the printing density is excellent, and the protective layer transferability is excellent. The light resistance is also good, and a high-quality printed product can be obtained.

It is sectional drawing which shows typically an example of the thermal transfer sheet used for the combination of this invention, and the image forming method of this invention. It is sectional drawing which shows typically another example of the thermal transfer sheet used for the combination of this invention, and the image forming method of this invention. It is sectional drawing which shows typically an example of the thermal transfer image receiving sheet used for the combination of this invention, and the image forming method of this invention. It is sectional drawing which shows typically another example of the thermal transfer sheet used for the combination of this invention, and the image forming method of this invention.

Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the spirit thereof.
In the present invention, the “sheet” means a sheet and a film defined in JIS-K6900. According to the definition in JIS-K6900, a sheet is a thin and generally flat product whose thickness is small for the length and width, and a film is extremely small compared to the length and width and has a maximum thickness. An arbitrarily limited thin flat product, usually supplied in the form of a roll. Therefore, it can be said that a film having a particularly thin thickness among the sheets is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. Therefore, in the present invention, the meaning of both a thick sheet and a thin sheet is meant. Is defined as “sheet”.

The combination of the thermal transfer sheet and the thermal transfer image-receiving sheet according to the present invention comprises a thermal transfer sheet in which a dye layer is provided on one side of the substrate and a back layer is provided on the other side of the substrate, and another substrate In combination with a thermal transfer image-receiving sheet provided with a dye-receiving layer on one side thereof,
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The dye-receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.

  In the combination of the thermal transfer sheet and the thermal transfer image receiving sheet according to the present invention, as the thermal transfer sheet, at least one of the dye layers is 50% by mass or more and 100% by mass with respect to the total solid content of the binder resin as the binder resin. By using the one containing nitrocellulose within the following range, the dye transfer efficiency is high, and even when the ratio of the dye to the binder resin is increased to improve the printing density, the storage stability is improved. It is excellent. However, such a thermal transfer sheet using nitrocellulose deteriorates the releasability of the thermal transfer image-receiving sheet from the dye-receiving layer, causing thermal fusion between the dye layer and the dye-receiving layer, or from the dye-receiving layer. In many cases, peeling marks are formed on the printed material when the dye layer is peeled off, and there is a problem that the quality of the printed material is deteriorated due to heat fusion or peeling marks. In the present invention, for such a thermal transfer sheet, the dye-receiving layer is combined with a thermal transfer image-receiving sheet containing a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil. As a result, the quality of the printed matter such as heat fusion and peeling marks can be prevented, the transferability of the protective layer is excellent, and the light resistance can be improved.

  When vinyl chloride resin is selected as the binder resin for the dye-receptive layer and combined with amino-modified silicone oil, releasability from the dye layer containing nitrocellulose is improved and protection is achieved by adding a small amount of amino-modified silicone oil. It was found that the layer transferability can be improved. In the present invention, since the epoxy-modified silicone oil is further combined, the releasability from the dye layer containing nitrocellulose is further improved and the light resistance is improved. Moreover, since the combination of the amino-modified silicone oil and the epoxy group-modified silicone oil can react in the dye receiving layer, it is possible to suppress the silicone oil from being transferred to the dye layer of the thermal transfer sheet due to thermal diffusion during printing. Therefore, the amount of silicone oil added can be relatively reduced, which contributes to excellent protective layer transferability.

Hereinafter, the combination of the present invention and the thermal transfer sheet and thermal transfer image receiving sheet used in the image forming method of the present invention will be specifically described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the thermal transfer sheet used in the combination of the present invention and the image forming method of the present invention. FIG. 2 shows the combination of the present invention and the image forming method of the present invention. FIG. 3 is a schematic sectional view showing another example of the thermal transfer sheet used, and FIG. 3 is a schematic sectional view showing an example of the thermal transfer image receiving sheet used in the combination of the present invention and the image forming method of the present invention.

≪Thermal transfer sheet≫
First, the thermal transfer sheet used in the combination of the present invention and the image forming method of the present invention will be described. As shown in FIG. 1, a thermal transfer sheet (hereinafter sometimes referred to as a thermal transfer sheet used in the present invention) 10 used in the combination of the present invention and the image forming method of the present invention 10 is one surface of a substrate 1. Is provided with a dye layer 2 containing a dye and a binder resin, and a back layer 3 is provided on the other surface of the substrate. And in this invention, at least 1 sort (s) of the dye layer 2 contains a nitrocellulose within the range of 50 mass% or more and 100 mass% or less with respect to the solid content total amount of the said binder resin as the said binder resin, To do. In FIG. 1, a dye primer layer 4 is provided between the substrate 1 and the dye layer 2, but the dye primer layer 4 is an arbitrary configuration in the thermal transfer sheet 10 of the present invention. Further, a back primer layer (not shown) may be provided between the substrate 1 and the back layer 3.

(Base material)
The substrate 1 used in the thermal transfer sheet 10 of the present invention is an essential component in the thermal transfer sheet 10 of the present invention, and is provided to hold the dye layer 2 and the back layer 3. The material of the substrate 1 is not particularly limited, but it is desirable to have mechanical characteristics that can withstand the heat applied by the thermal head when the dye of the dye layer 2 is transferred onto the thermal transfer image-receiving sheet and does not hinder handling. Examples of such base materials include polyesters such as polyethylene terephthalate, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivatives, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polystyrene, acrylic, and polyvinyl chloride. , Polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoro Various plastic fills such as propylene, polychlorotrifluoroethylene, and polyvinylidene fluoride Or it can be given a seat. Moreover, the thickness of the base material 1 can be appropriately set according to the material so that the strength and heat resistance thereof are appropriate, and is generally about 2.5 μm to 100 μm, preferably 1 μm to 10 μm. .

(Dye layer)
The dye layer of the present invention is a layer formed by supporting a dye with a binder resin. In the form shown in FIG. 1, one (single) dye layer 2 is provided on one surface of the substrate 1. However, as shown in FIG. 2, two or more dye layers are used. Can be repeatedly provided on the same surface of the same substrate 1 in the surface order (for example, Y (yellow) dye layer, M (magenta) dye layer, C (cyan) dye layer in FIG. 2)). Moreover, it is good also as providing a transferable protective layer on the same surface of the same base material 1 (for example, OP layer of FIG. 2). At least one of the dye layers used in the present invention contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin. is there.

<Dye>
As the dye material contained in the dye layer 2, conventionally known dyes can be used, but those having good characteristics as a printing material, for example, having a sufficient coloring density, light, heat, temperature, etc. Those which do not discolor due to are preferred. Examples of sublimable dyes that can be used for the dye layer 2 of the sublimation thermal transfer sheet include methine series such as diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, pyrazolone methines, and pyridone methines. Dyes, indoaniline dyes, indonaphthol dyes, acetophenone azomethine, pyrazoloazomethine, pyrazolone azomethine, pyrazolotriazole azomethine, imidazole azomethine, imidazoazomethine, pyridone azomethine and other azomethine dyes, xanthene dyes, oxazine dyes, Cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzeneazo dyes, pyridoneazo, thiophenazo, thiazoleazo, iso Azo azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, disazo azo dyes, spiropyran dyes, indolinospiropyran dyes, fluorane dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, Examples include quinophthalone dyes, aminopyrazole dyes, pyrazolotriazole dyes, styryl dyes such as dicyanostyryl and tricyanostyryl. Specifically, red dyes such as MSRedG (manufactured by Mitsui Toatsu Chemical Co., Ltd.), Macrolex Red Violet R (manufactured by Bayer), CeresRed 7B (manufactured by Bayer), Samalon Red F3BS (manufactured by Mitsubishi Chemical), and holon brilliant yellow Yellow dyes such as 6GL (manufactured by Clariant), PTY-52 (manufactured by Mitsubishi Kasei), Macrolex Yellow 6G (manufactured by Bayer), Kayaset Blue 714 (manufactured by Nippon Kayaku Co., Ltd.), Waxoline Blue AP-FW ( ICI), Holon Brilliant Blue SR (Sand), MS Blue 100 (Mitsui Toatsu Chemical), C.I. I. Blue dyes such as Solvent Blue 22 are listed.

<Binder resin>
In the dye layer 2, a binder resin for holding the dye is used together with the dye. At least one of the dye layers used in the present invention contains nitrocellulose as a binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin. The total solid content of the binder resin means the total solid content of the binder resin containing nitrocellulose in one kind of dye layer containing nitrocellulose. That is, when two or more types of dye layers are provided in the surface order, at least one type of dye layer is a dye layer containing nitrocellulose, and at least one other type is a dye layer containing no nitrocellulose. In the dye layer containing at least one nitrocellulose, the binder resin may contain nitrocellulose within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin. That's fine. For example, in combination with a binder resin containing nitrocellulose within a range of 50% by mass or more and 100% by mass or less with respect to the total solid content of the binder resin for at least one dye which is difficult to achieve a high printing density As a result, the printing density can be improved even for dyes that are difficult to achieve high printing density. And when including at least one dye layer containing nitrocellulose within the range of 50% by mass or more and 100% by mass or less with respect to the total solid content of the binder resin, the above-mentioned problems of thermal fusion and peeling marks Therefore, it is preferable to combine with the specific thermal transfer image receiving sheet. However, even when nitrocellulose is contained in an amount that does not reach 50% by mass or more based on the total solid content of the binder resin, depending on the dye, a sufficient print density may be achieved, so in at least one kind of dye layer If the binder resin contains nitrocellulose within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin, the binder resin in another dye layer containing nitrocellulose. Nitrocellulose may be contained in a range of less than 50% by mass with respect to the total solid content. Even in this case, in order to obtain the effect of containing nitrocellulose, it is preferable to contain 20% by mass or more of nitrocellulose with respect to the total solid content of the binder resin.

[Nitrocellulose]
Nitrocellulose as a binder resin has a high dye-holding power, so even if the mass ratio of dye to nitrocellulose (D / B ratio (dye / binder resin)) (hereinafter referred to as D / B ratio) increases, storage stability It is possible to satisfy the characteristics, and it is possible to prevent the occurrence of soiling, kick and back. Further, since the dye transfer efficiency is good, a high print density can be obtained even when the coating amount is reduced to increase the transfer efficiency.

  Although there is no particular limitation on the viscosity of nitrocellulose, when the dye layer 2 contains nitrocellulose having a viscosity of less than 1/16 according to JIS K-6703, the storage stability tends to decrease. On the other hand, when the dye layer 2 contains nitrocellulose having a viscosity of more than 120 according to JIS K-6703, there is a possibility that ink mist or the like may be generated when the dye layer 2 is formed.

  Considering this point, the dye layer 2 preferably contains 1/16 or more and 120 or less nitrocellulose in viscosity according to JIS K-6703, and contains 1/8 or more and 120 or less nitrocellulose. More preferably.

  As the nitrocellulose having a viscosity within the above range, a commercially available product can be used as it is. Examples of the viscosity within the above range include, for example, the types and viscosity symbols specified in JIS K-6703 manufactured by Taihei Chemicals Co., Ltd., H1 / 16, H1 / 8, L1 / 8, H1 / 4. Examples include L1 / 4, H1 / 2, H1 ″, H5 ″, H20, H60, and H120. In addition, DHX3-5, DHX5-10, DHX8-13, DHX11-16, DHX30-50, DHX40-70, DHL25-45, DHL120-170, H20 (160-210) manufactured by Inabata Sangyo Co., Ltd. , DHM10-25, SL-1, DLX3-5, DLX5-8, DLX8-13, DLX30-50, etc. can also be used.

  Nitrocellulose preferably has a nitrogen content (nitrification degree) of 10% or more. In consideration of handling safety, the nitrogen content is preferably 12.3% or less. By containing nitrocellulose having a nitrogen content of 10% or more in the dye layer 2, further improvement in transfer efficiency is expected.

[Other binder resins]
The binder resin for the dye layer may contain only nitrocellulose, and may contain other binder resins together with nitrocellulose. The content of the other binder resin needs to be in a range that does not hinder the content of the predetermined range of nitrocellulose with respect to the total solid content of the binder resin. In addition, in the case where two or more kinds of dye layers are provided in the surface order, a dye layer containing only another binder resin as a binder resin may be included.

  Examples of other binder resins include polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin, ethyl cellulose resin, methyl cellulose resin, cellulose acetate resin, cellulose butyrate resin, cellulose acetate propionate, cellulose acetate butyrate, and polyvinyl acetate resin. And vinyl resins such as polyacrylamide resins, polyester resins and the like. In addition, these binder resins may be used independently and can also be used in combination of 2 or more type.

  In addition to the dye and the binder resin, the dye layer 2 may contain additives such as inorganic fine particles and organic fine particles. Examples of the inorganic fine particles include carbon black, aluminum, and molybdenum disulfide. Examples of the organic fine particles include polyethylene wax. Further, the dye layer 2 may contain other release agents within a range not impeding the gist of the present invention. Examples of other release agents include conventionally known silicones and phosphate esters.

  The method for forming the dye layer 2 is not particularly limited, and a dye, a binder resin containing nitrocellulose, and additives such as a mold release agent and inorganic fine particles as necessary are added to toluene, methyl ethyl ketone, isopropyl alcohol, Gravure printing, die coating printing, bar coating printing, screen printing, reverse roll coating printing using a gravure plate, etc. dissolved in an appropriate organic solvent such as ethanol, cyclohexanone, DMF, or dispersed in an organic solvent or water It can be formed by applying and drying by the means described above.

Moreover, in this invention, it is preferable that the coating amount of the dye layer 2 shall be the range of 0.50 g / m < ² > or less at the time of drying. By making the coating amount of the dye layer 2 within this range, the dye transfer efficiency at the time of transfer can be improved, and the dye contained in the dye layer 2 can be transferred onto the thermal transfer image receiving sheet without waste, In addition, the storage stability requirement can be satisfied. If the coating amount of the dye layer 2 exceeds 0.50 g / m ² at the time of drying, the dye transfer efficiency may be lowered. The lower limit value of the dye layer 2 is not particularly limited, but when the coating amount of the dye layer is less than 0.13 g / m ² at the time of drying, the blending ratio of the sublimable dye to the nitrocellulose may be increased. In some cases, sufficient print density cannot be obtained. Therefore, considering this point, the coating amount of the dye layer is preferably 0.13 g / m ² or more 0.50 g / m ² or less at the time of drying.

If the content of the dye contained in the dye layer 2 is small, a sufficient print density may not be obtained. Considering this point, in one kind of dye layer containing nitrocellulose within the range of 50% by mass or more and 100% by mass or less with respect to the total solid content of the binder resin, the dye contained in the binder resin and the binder resin The mass ratio (D / B ratio (dye / binder resin)) is preferably 1.8 or more from the viewpoint that a printed matter having a sufficient printing density can be obtained.
In addition, when the D / B ratio is usually 1.8 or more, the conventionally known binder resin that has been used so far cannot retain the sublimable dye, but the total solid content of the binder resin In one type of dye layer containing nitrocellulose within a range of 50% by mass or more and 100% by mass or less, the D / B ratio is 1.8 or more because the dye layer 2 contains a predetermined amount of nitrocellulose. However, the dye can be retained sufficiently and is excellent in storage stability. Although there is no particular limitation on the preferable upper limit value of the D / B ratio, when the D / B ratio exceeds 3.5, the amount of the dye with respect to the binder resin is too large, and the binder cannot hold the dye, so that the storage stability is maintained. May decrease. Therefore, considering this point, the D / B ratio is preferably in the range of 1.8 or more and 3.5 or less, and more preferably in the range of 2.0 or more and 3.5 or less.

(Dye primer layer)
In the present invention, a dye primer layer 4 is preferably provided between the substrate 1 and the dye layer 2. By providing the dye primer layer 4, the adhesion between the substrate 1 and the dye layer 2 can be improved, and abnormal transfer of the dye layer 2 to the thermal transfer image receiving sheet during thermal transfer can be prevented.

  Examples of the resin constituting the dye primer layer 4 include polyester resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, hydroxyethyl cellulose, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamides. Resins, polyamide resins, polyether resins, polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, and the like.

  Moreover, the dye primer layer 4 can also be comprised from a colloidal inorganic pigment ultrafine particle. This not only prevents abnormal transfer of the dye layer 2 to the thermal transfer image receiving sheet at the time of thermal transfer, but also prevents migration of the dye from the dye layer 2 to the dye primer layer 4 at the time of printing, to the receiving layer side of the thermal transfer image receiving sheet. Dye diffusion can be performed effectively and the print density can be increased.

  As the colloidal inorganic pigment ultrafine particles, conventionally known compounds can be used. For example, silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or its hydrate, suspect boehmite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, oxidation Examples include titanium. In particular, colloidal silica and alumina sol are preferably used. These colloidal inorganic pigment ultrafine particles have a primary average particle size of 100 nm or less, preferably 50 nm or less.

The dye primer layer 4 is a gravure coating method, a roll coating method, a screen printing method, a gravure plate, and a primer layer coating solution prepared by dissolving or dispersing colloidal inorganic pigment ultrafine particles in an appropriate solvent. It can be formed by coating and drying by a conventionally known forming means such as the reverse roll coating method used. The coating amount of the primer layer coating solution is preferably about 0.02 to 1.0 g / m ² .

(Back layer)
As shown in FIG. 1, a back layer 3 is provided on the other surface of the substrate 1 for improving heat resistance and running performance of the thermal head during printing.

  The back layer 3 can be formed by appropriately selecting a conventionally known thermoplastic resin or the like. As such a thermoplastic resin, for example, polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins, and other polyolefin resins, Polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin, polyvinyl acetoacetal resin, etc. Examples thereof include thermoplastic resins such as polyvinyl acetal resin, and silicone modified products thereof.

  Moreover, you may add a hardening | curing agent to above-described resin. As the polyisocyanate resin that functions as a curing agent, conventionally known ones can be used without any particular limitation. Among them, it is desirable to use an adduct of an aromatic isocyanate. As the aromatic polyisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, Examples include p-phenylene diisocyanate, trans-cyclohexane-1,4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) thiophosphate, particularly 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Or, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is preferable. Such a polyisocyanate resin crosslinks the above-mentioned hydroxyl group-containing thermoplastic resin using the hydroxyl group, thereby improving the coating strength and heat resistance of the back layer.

  In addition to the above thermoplastic resin, the back layer 3 has a release agent such as wax, higher fatty acid amide, phosphoric ester compound, metal soap, silicone oil, surfactant, etc., fluorine for the purpose of improving slip properties. It is preferable that various additives such as organic powders such as resin, inorganic particles such as silica, clay, talc, calcium carbonate and the like are contained, and it is particularly preferable that at least one kind of phosphate ester or metal soap is contained. preferable.

The back layer 3 is formed on the surface of the substrate 1 opposite to the dye layer 2 by, for example, applying a coating liquid in which the thermoplastic resin and various additives added as necessary are dispersed or dissolved in an appropriate solvent. Further, it can be formed by applying and drying by a known means such as a gravure printing method, a screen printing method, a reverse roll coating printing method using a gravure plate. The coating amount of the back layer 3, from the viewpoint of improvement of such as heat resistance, it is preferable that drying after coating weight of 3 g / m ² or less, and more preferably to 0.1-2 g / m ² .

(Transferable protective layer)
Further, in the thermal transfer sheet of the present invention, the dye layer and the transferable protective layer described above can be provided in the surface order (for example, FIG. 4 shown in the below-described Examples).

  The transferable protective layer may have a multilayer structure or a single layer structure. In the case of a multi-layer structure, in addition to the main protective layer as a main component for imparting various durability to the image, the transferable protective layer is used to enhance the adhesion between the transferable protective layer and the image receiving surface of the print. An adhesive layer disposed on the outermost surface, an auxiliary protective layer, a layer for adding a function other than the function of the protective layer body, and the like may be included. The order of the main protective layer and other layers is arbitrary, but usually other layers are placed between the adhesive layer and the main protective layer so that the main protective layer becomes the outermost surface layer of the image receiving surface after transfer. To do.

  The main protective layer or the single-layered transferable protective layer constituting the multi-layered transferable protective layer can be formed of various resins conventionally known as protective layer forming resins. Examples of the resin for forming the protective layer include polyester resins, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, resins obtained by silicone-modifying these resins, mixtures of these resins, ionizing radiation curable resins, An ultraviolet blocking resin can be exemplified.

  The protective layer containing the ionizing radiation curable resin is particularly excellent in plasticizer resistance and scratch resistance. As the ionizing radiation curable resin, known ones can be used. For example, a radical polymerizable polymer or oligomer is crosslinked and cured by ionizing radiation irradiation, and a photopolymerization initiator is added if necessary, and an electron beam Those obtained by polymerization and crosslinking with ultraviolet rays can be used.

  The main purpose of the protective layer containing the ultraviolet blocking resin is to impart light resistance to the printed material. As the ultraviolet blocking resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber with a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, addition-polymerizable double-reactive organic UV absorbers such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines, etc. Examples thereof include those in which a reactive group such as a bond (for example, a vinyl group, an acryloyl group, a methacryloyl group), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group is introduced.

  The main protective layer provided in the single-layered transferable protective layer or the multi-layered transferable protective layer usually has a thickness of about 0.5 to 10 μm, although it depends on the type of protective layer-forming resin. Preferably there is.

  An adhesive layer may be formed on the outermost surface of the transferable protective layer. The adhesive layer should be formed of a resin having good adhesiveness when heated, such as acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyamide resin. Can do. The thickness of the adhesive layer is usually about 0.1 to 5 μm. Further, the dye primer layer may be formed at an arbitrary position in the multilayer structure of the transferable protective layer.

≪Thermal transfer image receiving sheet≫
Next, the combination of the present invention and the thermal transfer image receiving sheet used in the image forming method of the present invention (hereinafter sometimes referred to as the thermal transfer image receiving sheet used in the present invention) will be described. As shown in FIG. 3, the thermal transfer image receiving sheet 20 used in the present invention has a configuration in which a dye receiving layer 12 is provided on one surface of another substrate 11. In FIG. 3, the heat insulating layer 13 is provided between the other substrate 11 and the dye receiving layer 12, but the heat insulating layer 13 has an arbitrary configuration in the thermal transfer image receiving sheet 20 used in the present invention. is there. Hereinafter, each configuration of the thermal transfer image receiving sheet 20 will be specifically described.

(Other base materials)
The other substrate used in the thermal transfer image-receiving sheet of the present invention is not particularly limited as long as it supports the dye-receiving layer and other layers provided as necessary and can withstand the heating during thermal transfer.
There is no particular limitation on the other base material 11, and stretched or unstretched plastics such as polyolefin, polyester, polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyamide, polymethylpentene and the like having high heat resistance such as polyethylene terephthalate and polyethylene naphthalate Films and white opaque films formed by adding white pigments and fillers to these synthetic resins can also be used. In addition, materials such as high-quality paper, coated paper, art paper, cast coated paper, and paperboard can also be used. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper or cellulose synthetic paper, plastic film, and synthetic paper. In the present invention, a commercially available base material can be used, for example, RC paper paper ( Mitsubishi Paper Industries, Ltd., trade name: STF-150) and the like are preferable. In the present specification, the base material constituting the thermal transfer image-receiving sheet 20 is referred to as another base material 11 in order to distinguish it from the base material 1 constituting the thermal transfer sheet. 1 and the other substrate 11 constituting the thermal transfer image receiving sheet 20 may be the same or different.

  The thickness of the other substrate can be appropriately selected depending on the material so that its strength, heat resistance, etc. are appropriate, but it is usually about 1 μm to 300 μm, preferably about 60 μm to 200 μm.

(Dye-receiving layer)
The dye receiving layer in the present invention is for receiving the dye transferred from the thermal transfer sheet and maintaining the formed image. The dye receiving layer in the present invention is characterized by containing a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.
Since the dye-receiving layer contains a combination of the above three specific components, even when combined with a thermal transfer sheet equipped with a dye layer containing nitrocellulose, thermal fusing and peeling marks can be suppressed, while protective layer transfer In addition, the light resistance of the printed material can be improved. Further, the dye acceptability is high, and a printed matter having a high printing density can be obtained.

<Vinyl chloride resin>
The vinyl chloride resin is a polymer containing a structural unit derived from vinyl chloride. The vinyl chloride resin used in the present invention may consist only of vinyl chloride-derived structural units, or may be a copolymer of vinyl chloride and a copolymerizable monomer. In the present invention, a copolymer including a structural unit derived from vinyl chloride and a structural unit derived from another monomer is particularly preferable. For example, it is easy to adjust the releasability, print density, etc. of the receiving layer used in the present invention within a desired range by appropriately selecting and adjusting the types of other structural units and the copolymerization ratio. Because it becomes.
In the present invention, the vinyl chloride resin is selected as the binder resin of the dye-receiving layer, so that the effect of preventing heat fusion with the dye layer containing nitrocellulose is enhanced, and excellent protective layer transferability is obtained. Is estimated to be possible.

  The monomer copolymerized with vinyl chloride is not particularly limited as long as it can be copolymerized with vinyl chloride, vinyl alcohol derivatives such as vinyl acetate, vinyl alcohol, vinyl propionate; acrylic acid and methacrylic acid and their methyl, ethyl, propyl Acrylic acid and methacrylic acid esters such as butyl, 2-ethylhexyl ester; maleic acid derivatives such as maleic acid, diethyl maleate, dibutyl maleate, dioctyl maleate; vinyl ether derivatives such as methyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether Acrylonitrile, methacrylonitrile, styrene and the like are mentioned, and vinyl acetate is particularly preferable as the copolymer component.

  Accordingly, vinyl chloride-vinyl acetate copolymer is particularly preferably used as the vinyl chloride resin used in the dye-receiving layer. As the vinyl chloride-vinyl acetate copolymer, structural units derived from vinyl chloride and acetic acid are used. Not only in the case of a copolymer containing only vinyl-derived constitutional units, but also in a range not impeding the object of the present invention, constitutional units derived from acrylic acid and methacrylic acid derivatives, constitutional units derived from vinyl alcohol, constitutions derived from maleic acid It may include a unit or the like. Specific examples include vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, ethylene-vinyl chloride-acrylic acid ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, and the like. be able to. The component ratio of vinyl chloride and vinyl acetate in the copolymer may be any ratio, but the vinyl chloride component is preferably 50% by mass or more in the copolymer. Especially, it is preferable that the mass ratio of the component of vinyl chloride and vinyl acetate is 85 / 15-90 / 10. Moreover, it is preferable that components other than vinyl chloride and vinyl acetate mentioned above are 10 mass% or less.

  As a commercial product of vinyl chloride resin, for example, vinyl chloride-vinyl acetate copolymer may be mentioned. Solvain C, sorbine CL, sorbine CH, solvine CN, solvine C5, solvine M, solvine MF, solvine A, solvine A, solvine TA5R, Solvain TAO, Solvain MK6, Solvain TA2 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), ESREC A, ESREC C, ESREC M (all trade names, manufactured by Sekisui Chemical Co., Ltd.), Vinylite VAGH, VINYLITE VYHH, VINYLITE VMCH, VINYLITE VYHD, VINYLITE VYLF, VINYLITE VYNS, VINYLITE VMCC, VINYLITE VMCA, VINYLITE VAGD, VINYLITE VERR, VINYLITE VROH (all trade names, union car) Produced by id Co., Ltd.), DENKAVINYL 1000GKT, DENKAVINYL 1000L, DENKAVINYL 1000CK (all trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.), and the like.

The molecular weight of the vinyl chloride resin used in the present invention is not particularly limited as long as the releasability of the dye-receiving layer in the present invention is within a desired range, but the number average molecular weight is particularly high. , Preferably 30000 or more, more preferably 35000 or more. This is because by using a vinyl chloride resin having a number average molecular weight within such a range, the releasability of the dye-receiving layer used in the present invention can be further improved.
In addition, the vinyl chloride resin used in the present invention may be only one type or two or more types.
The content of the vinyl chloride resin is preferably 70% by mass or more and 100% by mass or less (in terms of solid content), more preferably 80% by mass or more and 99% by mass or less, based on the total dye receiving layer material. In the present invention, the “solid content” means all components other than the solvent.

<Silicone oil>
The silicone oil used in the present invention contains an epoxy-modified silicone oil and an amino-modified silicone oil as essential components. When the amino-modified silicone oil is combined with a vinyl chloride resin, the releasability with respect to the dye layer containing nitrocellulose can be improved by adding a small amount. In the present invention, since the epoxy-modified silicone oil is further combined, the releasability with respect to the dye layer containing nitrocellulose is further improved, thermal fusion, peeling marks and the like are suppressed, and light resistance is improved. The light resistance of the dye may be deteriorated due to the interaction between the dyes, and the light resistance tends to be improved by increasing the distance between the dye molecules. It is presumed that the epoxy-modified silicone oil functions like a plasticizer in a vinyl chloride resin. As a result, the dye molecules after transfer are likely to penetrate deep into the dye receiving layer, and the distance between the dye molecules can be increased, so that it is presumed that the light resistance of the dye can be improved. In addition, the amino-modified silicone oil can improve the releasability from the dye layer containing nitrocellulose only by adding a small amount to the vinyl chloride resin and can react with the epoxy-modified silicone oil. It is possible to make the addition amount small, and it is difficult to inhibit the transferability of the protective layer.

  The epoxy-modified silicone oil has an epoxy group at the side chain or terminal in the silicone oil. Specific examples include those in which at least one of a side chain and a main chain terminal group of a linear dimethylpolysiloxane, which is a kind of silicone oil, is substituted with an epoxy group. Furthermore, it may contain a substituent such as a phenyl group or an aralkyl group. The epoxy group may be an alicyclic epoxy group.

  The epoxy-modified silicone oil preferably further includes an aralkyl group from the viewpoint of light resistance.

  A commercial item can also be used as said epoxy modified silicone oil, for example, X-22-3000T (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned.

  The epoxy-modified silicone oil is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less based on the total solid content of the dye receiving layer.

On the other hand, the amino-modified silicone oil has an amino group at the side chain or terminal in the silicone oil. Specific examples include one in which at least one of a side chain and a main chain terminal group of linear dimethylpolysiloxane, which is one kind of silicone oil, is substituted with an amine. Furthermore, it may contain a substituent such as a phenyl group or an aralkyl group. As the amine to be replaced, monoamine (-RNH ₂₎ as well, may be diamine _{(-RN (H) R'NH 2)} .

  The amino-modified silicone oil preferably has a diamine in terms of light resistance, and more preferably has a diamine in the side chain in terms of the number of functional groups.

  A commercial item can also be used as said amino modified silicone oil, For example, KF-861, KF-8004, KF-864 (above, Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

  The amino-modified silicone oil is preferably 0.5% by mass or more and 4% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less, based on the total solid content of the dye receiving layer. .

  In the present invention, the silicone oil may further contain other silicone oils in addition to the epoxy-modified silicone oil and the amino-modified silicone oil as long as the effects of the present invention are not impaired. Examples of other silicone oils include modified silicone oils such as alkyl-modified silicone oil, fluorine-modified silicone oil, phenyl-modified silicone oil, polyether-modified silicone oil, vinyl-modified silicone oil, and hydrogen-modified silicone oil. From the viewpoint that the effects of the present invention are sufficiently exerted, the other silicone oil is preferably used at 8% or less of the total amount of the silicone oil used in the present invention.

  The addition amount of the silicone oil is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total solid content of the dye receiving layer.

<Other ingredients>
In addition to the above, as an optional compound that can be added to the dye-receiving layer within a range that does not interfere with the effects of the present invention, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a pigment, an antistatic agent, Examples thereof include a plasticizer and a hot-melt material. Moreover, you may use together mold release agents other than a silicone oil in the range which does not prevent the effect of this invention. Examples of such a release agent include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorine-based or phosphate-based surfactant, and the like. In addition, a binder resin other than the vinyl chloride resin may be used in combination as long as the effects of the present invention are not hindered. Examples of such a binder resin include polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin, ethyl cellulose resin, methyl cellulose resin, cellulose acetate resin, cellulose butyrate resin, cellulose acetate propionate, cellulose acetate butyrate, and polyvinyl acetate. Examples thereof include vinyl resins such as resins and polyacrylamide resins, and polyester resins. Even when a binder resin other than the vinyl chloride resin is used in combination, the vinyl chloride resin is the main component of the binder resin, that is, 50% by mass or more of the total of the binder resin, and further the total of the binder resin. It is preferably 70% by mass or more, and more preferably 90% by mass or more.

In forming the dye-receiving layer, the coating amount of the dye-receiving layer coating solution is not particularly limited, but is preferably 0.5 to 10 g / m ^{2 in} a dry state.

(Insulation layer)
A heat insulating layer 13 may be provided between the other substrate 11 and the water-based dye receiving layer 12. By providing the heat insulating layer 13, it is possible to prevent the heat applied from the thermal head to the aqueous dye-receiving layer 12 from being transferred to the other base material 11 and the like, thereby preventing the print density from being lowered. Hereinafter, although an example of a heat insulation layer is demonstrated, in addition to this, conventionally well-known things called "heat insulation layer", "hollow layer", and "hollow particle layer" can be selected suitably, and can be used.

  The heat insulating layer 13 generally contains hollow particles having a function of imparting heat insulating properties and cushioning properties. The hollow particles may be expanded particles or non-expanded particles. Further, the expanded particles may be independent expanded particles or continuous expanded particles. Furthermore, the hollow particles may be organic hollow particles composed of resin or the like, or inorganic hollow particles composed of glass or the like. The hollow particles may be cross-linked hollow particles. The hollow portion may contain air or gas. Examples of the gas include methane gas and butane gas.

  Examples of the resin constituting the hollow particles include styrene resins such as crosslinked styrene-acrylic resins, (meth) acrylic resins such as acrylonitrile-acrylic resins, phenolic resins, fluorine resins, polyamide resins, and polyimide resins. And polycarbonate resins and polyether resins. The average particle diameter of the hollow particles is not particularly limited as long as the desired heat insulating property and cushioning property can be imparted to the heat insulating layer depending on the type of resin constituting the hollow particles, but is usually 0. It is preferably within the range of 1 μm to 15 μm, particularly preferably within the range of 0.1 μm to 10 μm. This is because if the average particle size is too small, the amount of hollow particles used increases and the cost increases, and if the average particle size is too large, it becomes difficult to form a smooth heat insulating layer.

  In the present invention, the amount of the hollow particles contained in the heat insulating layer 13 is not particularly limited as long as a heat insulating layer having desired heat insulating properties and cushioning properties can be obtained, for example, 30% by mass to 90% by mass. It is preferable to be within the range of 50% by mass to 80% by mass. This is because if the content is too small, the gaps in the heat insulating layer are reduced, and sufficient heat insulating properties and cushioning properties may not be obtained. If the content is too large, the adhesiveness is inferior.

  The heat insulation layer may be a porous layer having fine voids inside the thermoplastic resin. As the thermoplastic resin, polyolefin resin and polyester resin are preferable, polyolefin resin is more preferable, and polyethylene and polypropylene are particularly preferable. For the formation of the porous layer, a porous film is preferably used.

  In a porous film, as a method for producing fine voids in the film, a method of producing by using a compound in which organic fine particles or inorganic fine particles (one kind or plural kinds) are incompatible with the resin serving as a base of the film is kneaded. Can be adopted. When this compound is viewed microscopically, the base resin and fine particles incompatible with the base resin form a fine sea-island structure. The fine voids as described above are generated by separation of the interface or large deformation of the region forming the island.

  As a method for forming the fine voids, for example, a method in which polypropylene is mainly used and polyester or acrylic resin having a melting point higher than that of polypropylene is added thereto. In this case, polyester or acrylic resin serves as a nucleating agent that forms fine voids. It is preferable that content of the polyester and acrylic resin is 2-10 mass parts with respect to 100 mass parts of polypropylene in any case. When the content is 2 parts by mass or more, fine voids can be sufficiently generated, and the printing sensitivity can be further improved. Moreover, when content is 10 mass parts or less, the heat resistance of a porous film can fully be ensured.

  Moreover, when producing the porous film which uses polypropylene as the base resin, it is preferable to add polyisoprene in order to generate more fine and dense voids. Thereby, higher printing sensitivity can be obtained. For example, a porous film having high printing sensitivity can be obtained by preparing a compound mainly composed of polypropylene, blended with acrylic resin or polyester, and polyisoprene, forming a compound, and stretching.

(Middle layer)
In the thermal transfer image receiving sheet of the present invention, an intermediate layer may be provided between the heat insulating layer 13 and the dye receiving layer 12. The intermediate layer is intended to provide adhesion between the heat-insulating layer and the dye-receiving layer, whiteness, cushioning property, concealing property, antistatic property, anti-curling property and the like. As the intermediate layer, any conventionally known intermediate layer can be provided. The binder resin contained in the intermediate layer is polyurethane resin, polyester resin, polycarbonate resin, polyamide resin, acrylic resin, polystyrene resin, polysulfone resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride. -Vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin, epoxy resin, cellulose resin, ethylene-vinyl acetate copolymer resin, polyethylene resin, polypropylene resin, etc. Of these resins, those having an active hydroxyl group may be further cured with those isocyanates.

In addition, fillers such as titanium oxide, zinc oxide, magnesium carbonate, and calcium carbonate can be added to the intermediate layer in order to impart whiteness and concealment. In addition, stilbene compounds, benzimidazole compounds, benzoxazole compounds, etc. are added to the intermediate layer as fluorescent brighteners to increase whiteness, or hindered amine compounds are used to increase the light resistance of printed materials. , Hindered phenol compounds, benzotriazole compounds, benzophenone compounds, etc. as UV absorbers or antioxidants, or cationic acrylic resins, polyaniline resins, and various conductive materials to impart antistatic properties A filler or the like can be added. The coating amount of the intermediate layer is not particularly limited, but is preferably about 0.5 to 5 g / m ^{2 in} a dry state.

In addition, a back surface layer having a function of improving the transferability of the thermal transfer image receiving sheet and a function of preventing curling can be provided on a surface different from the surface on which the dye receiving layer 12 of the other substrate 11 is provided.
As described above, the thermal transfer image-receiving sheet 20 used in the present invention has only to have the specific dye-receiving layer 12 as an essential configuration, and any other functional layers are not limited in any way. Absent. These various functional layers may be appropriately selected from conventionally known ones.

(Image forming method)
The image forming method according to the present invention includes a thermal transfer sheet in which a dye layer is provided on one surface of a substrate and a back layer is provided on the other surface of the substrate, and a dye on one surface of the other substrate. An image forming method for forming an image on the thermal transfer image receiving sheet using in combination with a thermal transfer image receiving sheet provided with a receiving layer,
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The dye-receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.

  That is, the image forming method of the present invention is a combination of the thermal transfer sheet 10 having the dye layer containing nitrocellulose described in the combination of the present invention and the thermal transfer image receiving sheet 20 having the specific dye receiving layer. It is characterized in that an image is formed. The dye layer 2 of the thermal transfer sheet 10 described above and the dye receiving layer 12 of the thermal transfer image receiving sheet 20 are overlapped, and the thermal transfer head 10 is used from the back side of the thermal transfer sheet 10. Image formation is performed by applying heat and transferring the dye contained in the dye layer 2 to the dye receiving layer 12.

Thermal transfer sheets using nitrocellulose have high dye transfer efficiency and excellent storage stability even when the ratio of dye to binder resin is increased to improve printing density. In many cases, the releasability from the layer deteriorates and the dye layer and the dye-receiving layer cause heat fusion, or when the dye layer is peeled off from the dye-receiving layer, the printed matter may be peeled off. There has been a problem that the quality of the printed matter is deteriorated due to fusing or peeling marks. As described above, in the present invention, such a thermal transfer sheet is combined with a thermal transfer image receiving sheet in which the dye receiving layer contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil. Therefore, it is possible to suppress the heat fusion and peeling trace as described above, and on the other hand, the protective layer transferability is excellent and the light resistance can be improved without adversely affecting the protective layer transferability. .
The thermal transfer sheet and thermal transfer image-receiving sheet used in the image forming method of the present invention are as described in the combination of the present invention, and detailed description thereof is omitted here.

Next, the present invention will be described more specifically with reference to examples and comparative examples. “Part” in the text is based on mass unless otherwise specified.
Example 1
(1) Preparation of thermal transfer sheet A polyethylene terephthalate film having a thickness of 5 μm was used as a base material, and a coating solution for the back layer having the following composition was applied and dried so as to be 0.5 g / m ² upon drying. A back layer was formed. Next, a coating liquid for the main protective layer of the transferable protective layer having the following composition is applied to a part of the surface opposite to the side on which the back layer of the substrate is provided, with a dry coating amount of 1.0 g / m ^2. Thus, the main protective layer for the transferable protective layer was formed in the region where the transferable protective layer was to be formed. Next, a dye primer layer coating solution having the following composition is applied to the entire surface of the substrate opposite to the side on which the back layer is provided, and dried to give 0.1 g / m ² when dried. A primer layer was formed. Next, a yellow dye layer coating liquid 1, a magenta dye layer coating liquid 1, a cyan dye layer coating liquid 1 having the following composition, and an adhesive layer coating for a transferable protective layer are formed on the primer layer. Coating solution, each dye layer is 0.6 g / m ² when dried, and the dry coating amount of the adhesive layer for transferable protective layer is 1.0 g / m ² . By drying, a yellow dye layer 1, a magenta dye layer 1, a cyan dye layer 1, and a protective layer transfer layer were formed to obtain a thermal transfer sheet of Example 1 as shown in FIG.

<Back layer coating liquid>
・ Polyvinyl acetal resin (ESREC KS-1 manufactured by Sekisui Chemical Co., Ltd.) 60.8 parts ・ Polyisocyanate (Barnock D750 manufactured by Dainippon Ink & Chemicals, Inc.) 4.2 parts ・ Zinc stearyl phosphate (LBT-1830) 10 parts by refining (manufactured by Sakai Chemical Industry Co., Ltd.) 10 parts by zinc stearate (SZ-PF by Sakai Chemical Industry Co., Ltd.)
・ Polyethylene wax (polywax 3000 Toyo Petrolite Co., Ltd.) 10 parts ・ Methyl ethyl ketone 200 parts ・ Toluene 100 parts

<Dye primer layer coating solution>
・ Alumina sol (solid content 10%) (manufactured by Nissan Chemical Industries) 30 parts ・ Polyvinylpyrrolidone resin (manufactured by K-90 ISP) 3 parts ・ Water 50 parts ・ Isopropyl alcohol 17 parts

<Yellow dye layer coating solution 1>
Disperse dye (Disperse Yellow 231) 2.5 parts Disperse dye (Yellow dye represented by the following chemical formula (A)) 2.5 parts Polyvinylacetoacetal resin (KS-5 manufactured by Sekisui Chemical Co., Ltd.) 2 8 parts polyethylene wax (ACumist 1204 Honeywell) 0.1 part methyl ethyl ketone 45.0 parts toluene 45.0 parts

<Coating liquid 1 for magenta dye layer>
・ Disperse dye (disperse thread 60) 1.5 parts ・ Disperse dye (dispers violet 26) 2.0 parts ・ Nitrocellulose resin (solid content 70% H40 equivalent, nitrification degree 11.7 to 12.2%) (DHM10 -25 Inabata Sangyo Co., Ltd.) 2.0 parts (solid content 1.4 parts)
・ Polyethylene wax (ACumist 1204 Honeywell) 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Cyan dye layer coating solution 1>
-Disperse dye (Solvent Blue 63) 2.5 parts-Disperse dye (Disperse Blue 354) 2.5 parts-Polyvinylacetoacetal resin (KS-5 manufactured by Sekisui Chemical Co., Ltd.) 4.5 parts-Polyethylene wax 0 .1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Coating liquid for main protective layer for transferable protective layer>
・ Acrylic resin 20 parts (Dianar BR87, manufactured by Mitsubishi Rayon Co., Ltd.)
・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

<Coating liquid for adhesive layer for transferable protective layer>
・ 20 parts of polyester resin (Byron 200 manufactured by Toyobo Co., Ltd.)
UV absorber copolymer resin 10 parts (UVA-635L manufactured by BASF)
・ Methyl ethyl ketone / toluene (mass ratio 1: 1) 80 parts

(2) Preparation of thermal transfer image-receiving sheet As a base material, a porous polyethylene film (Toyopearl SS P4255 Toyobo Co., Ltd.) is used as a heat insulating layer on RC base paper (155 g / m ² , thickness 151 μm) (Mitsubishi Paper Co., Ltd.). ) Product thickness 35 μm) was dry-laminated using a urethane adhesive (coating amount 5 g / m ² ) to obtain a support in which the base material and the heat insulating layer were laminated. Subsequently, the intermediate layer coating liquid 1 having the following composition was applied on the heat insulating layer side on the support so as to have a thickness of 1.0 g / m ² to form an intermediate layer. Next, a dye receiving layer coating solution 1 having the following composition is applied on the intermediate layer so as to have a thickness of 2.5 g / m ² to form a dye receiving layer, and the substrate / heat insulating layer / intermediate layer / dye is formed. A thermal transfer image receiving sheet of Example 1 in which the receiving layers were laminated in this order was obtained.

<Intermediate layer coating solution>
・ Polyester resin (Polyester WR-905 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 50 parts ・ Titanium oxide (manufactured by Tochem Products Co., Ltd.) 20 parts ・ Fluorescent whitening agent (Ubitex BAC Ciba Specialty Chemicals ( 1.2 parts / water / isopropyl alcohol = 1/1 (mass ratio) 28.8 parts

<Dye-receiving layer coating solution 1>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts / amino-modified silicone oil (side-chain diamine-modified, KF-861 Shin-Etsu Chemical Co., Ltd.) 1 part / methyl ethyl ketone (MEK) -toluene mixed solvent (mass ratio 1: 1) 500 parts

(Example 2)
In Example 1, the same procedure as in Example 1 except that a thermal transfer image-receiving sheet was formed using the dye-receiving layer coating solution 2 having the following composition for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image receiving sheet was obtained.
<Dye-receiving layer coating solution 2>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts amino modified silicone oil (side chain diamine modified, KF-861 Shin-Etsu Chemical Co., Ltd.) 2 parts MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Example 3)
In Example 1, the same procedure as in Example 1 except that a thermal transfer image-receiving sheet was formed using the dye-receiving layer coating solution 3 having the following composition for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image receiving sheet was obtained.
<Dye-receiving layer coating solution 3>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts / amino-modified silicone oil (side chain diamine-modified, KF-861 Shin-Etsu Chemical Co., Ltd.) 4 parts / MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

Example 4
In Example 1, the same procedure as in Example 1 except that a thermal transfer image-receiving sheet was formed using the dye-receiving layer coating liquid 4 having the following composition for the dye-receiving layer coating liquid. A combination of a thermal transfer sheet and a thermal transfer image receiving sheet was obtained.
<Dye-receiving layer coating solution 4>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts / amino-modified silicone oil (side chain diamine-modified, KF-861 Shin-Etsu Chemical Co., Ltd.) 5 parts / MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Example 5)
In Example 1, the dye receiving layer coating solution 5 was used in the same manner as in Example 1 except that a thermal transfer image receiving sheet was formed using the dye receiving layer coating solution 5 having the following composition. A combination of a thermal transfer sheet and a thermal transfer image receiving sheet was obtained.
<Dye-receiving layer coating solution 5>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Part amino-modified silicone oil (side chain diamine modified, KF-8004 Shin-Etsu Chemical Co., Ltd.) 2 parts MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Example 6)
In Example 1, the same procedures as in Example 1 except that a thermal transfer image-receiving sheet was formed using the dye-receiving layer coating solution 6 having the following composition for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image receiving sheet was obtained.
<Dye-receiving layer coating solution 6>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts / amino-modified silicone oil (side chain monoamine-modified, KF-864 Shin-Etsu Chemical Co., Ltd.) 2 parts / MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Comparative Example 1)
Comparative Example 1 was performed in the same manner as in Example 1 except that a thermal transfer image-receiving sheet was formed using the comparative dye-receiving layer coating solution 1 having the following composition in Example 1 for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image-receiving sheet was obtained.
<Comparative dye receiving layer coating solution 1>
・ Vinyl chloride resin (Vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Comparative Example 2)
Comparative Example 2 was carried out in the same manner as in Example 1 except that a thermal transfer image-receiving sheet was formed using the comparative dye-receiving layer coating solution 2 having the following composition in Example 1 for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image-receiving sheet was obtained.
<Comparative dye receiving layer coating solution 2>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5 Parts / MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Comparative Example 3)
Comparative Example 3 was carried out in the same manner as in Example 1 except that a thermal transfer image-receiving sheet was formed using the comparative dye-receiving layer coating solution 3 having the following composition in Example 1 for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image-receiving sheet was obtained.
<Comparative dye receiving layer coating solution 3>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Amino-modified silicone oil (side chain diamine-modified, KF-861 Shin-Etsu Chemical Co., Ltd.) 2 / MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

(Comparative Example 4)
Comparative Example 4 was performed in the same manner as in Example 1 except that a thermal transfer image-receiving sheet was formed using the comparative dye-receiving layer coating solution 4 having the following composition in Example 1 for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image-receiving sheet was obtained.
<Comparative dye receiving layer coating solution 4>
・ Polyester resin (Byron 103 Toyobo Co., Ltd.) 80 parts ・ Polymer plasticizer containing ethylene-derived structural unit (Elvalloy 741 Mitsui Dupont Polychemical Co., Ltd.) ・ Epoxy-modified silicone oil (side chain type, KF- 103 Shin-Etsu Chemical Co., Ltd.) 4 parts, amino-modified silicone oil (side-chain monoamine, both-end ethoxy-modified, KF-857 Shin-Etsu Chemical Co., Ltd.) 4 parts, MEK-toluene mixed solvent (mass ratio 1: 1) 500 copies

(Comparative Example 5)
Comparative Example 5 was performed in the same manner as in Example 1 except that a thermal transfer image-receiving sheet was formed using the comparative dye-receiving layer coating solution 5 having the following composition in Example 1 for the dye-receiving layer coating solution. A combination of a thermal transfer sheet and a thermal transfer image-receiving sheet was obtained.
<Comparative dye receiving layer coating solution 5>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin Solvein C Nissin Chemical Industry Co., Ltd.) 100 parts ・ Epoxy-modified silicone oil (side chain type, X-22-3000T Shin-Etsu Chemical Co., Ltd.) 5・ Polyether-modified silicone oil (X-22-4515, Shin-Etsu Chemical Co., Ltd.) 3 parts ・ MEK-toluene mixed solvent (mass ratio 1: 1) 500 parts

[Evaluation]
The combinations of the thermal transfer sheet and the thermal transfer image receiving sheet produced in each example and comparative example were evaluated as follows. The results are shown in Table 1.
(1) Releasability (1-1) Abnormal transfer property The produced thermal transfer sheet and thermal transfer image-receiving sheet were subjected to a sublimation thermal transfer printer (Citizen Systems Co., Ltd., model: CW-02) with an RGB value of 128/255. A gray image was printed, and it was evaluated whether abnormal transfer occurred in the printed matter (printing environment: temperature 0 ° C.). The abnormal transfer is a phenomenon in which, when printing, the thermal transfer sheet and the thermal transfer image receiving sheet are partially fused by heat, and a part of the dye layer is transferred to the printed matter together with the binder.
5: No abnormal transfer.
1: Abnormal transcription exists.

(1-2) Peeling Sound and Peeling Mark The produced thermal transfer sheet and thermal transfer image-receiving sheet are black solid images with an RGB value of 0/255 using a sublimation thermal transfer printer (Citizen Systems Co., Ltd., model: CW-02). Was peeled off and sensory evaluation was performed for the peeling sound during printing (printing environment: temperature 35 ° C., relative humidity 80%). The evaluation criteria are as follows.
5: No peeling sound.
4: I can hear a slight peeling sound, but I don't mind.
3: Peeling sound is generated, but no peeling mark is seen on the ribbon after printing.
2: Peeling sound is generated and peeling marks are seen on the ribbon after printing.
1: Peeling sound is generated, and severe peeling marks are seen on the ribbon after printing.

(2) Protective layer transfer property The produced thermal transfer sheet and thermal transfer image-receiving sheet were printed with a solid white image with an RGB value of 255/255 using a sublimation thermal transfer printer (Citizen Systems Co., Ltd., model: CW-02). Then, it was visually confirmed that there was no problem in transfer of the protective layer (printing environment: temperature 0 ° C.). The evaluation criteria are as follows.
5: The protective layer is transferred.
3: Part of the protective layer is not transferred 1: All of the protective layer is not transferred.

(3) Print density Using the produced thermal transfer image-receiving sheet, a gray-scale 18th floor with an RGB value of 15 * n (n = 0-17) using a sublimation thermal transfer printer (Citizen Systems Co., Ltd., model: CW-02). A gradation image was printed. The optical reflection density was measured with an optical densitometer (spectrolino manufactured by Gretag Macbeth), and the density of the portion (ODmax) to which the maximum energy was applied was measured.

(4) Light resistance evaluation method The produced thermal transfer image-receiving sheet is gray 18 having a RGB value of 15 * n (n = 0 to 17) using a sublimation thermal transfer printer (Citizen Systems Co., Ltd., model: CW-02). A gradation image was printed, and light resistance was evaluated using a xenon fade meter under the following conditions.
(I) Conditions for light resistance evaluation / irradiation tester: Ci4000 manufactured by Atlas
・ Light source: Xenon lamp ・ Filter: Inside = CIRA
Outside = soda lime black panel temperature: 45 (° C)
Irradiation intensity: measured value at 1.2 (W / m ² ) -420 (nm) Irradiation energy: integrated value at 300 (kJ / m ² ) -420 (nm)

(Ii) Light resistance evaluation Next, the change in optical reflection density before and after irradiation under the above light resistance conditions was measured with an optical densitometer (Spectrolino, manufactured by Gretag Macbeth), and the optical reflection density before irradiation was around 1.0. In this step, L *, a *, and b * were calculated, and the hue change (ΔE) was calculated using the following hue change equation.
(Hue change formula)
Δa = a * after storage-a * before storage
Δb = b * after storage−b * before storage
When
ΔE = (square of Δa + square of Δb) square root

(Summary of results)
In the combination of the thermal transfer sheet and thermal transfer image-receiving sheet obtained in Examples 1 to 6, the dye-receiving layer of the thermal transfer image-receiving sheet contains vinyl chloride resin, epoxy-modified silicone oil, and amino-modified silicone oil Therefore, while being excellent in printing density, heat fusion, peeling traces and the like were suppressed, and protective layer transferability was excellent, and light resistance was also good.
On the other hand, in the combination of the thermal transfer sheet and the thermal transfer image-receiving sheet obtained in Comparative Example 1, the dye-receiving layer of the thermal transfer image-receiving sheet was only a vinyl chloride resin, so that the releasability was poor and abnormal transfer was caused, which was terrible. Peeling marks were seen and the light resistance was also poor.
In the combination of the thermal transfer sheet and thermal transfer image-receiving sheet obtained in Comparative Example 2, the dye-receiving layer of the thermal transfer image-receiving sheet was obtained by adding only an epoxy-modified silicone oil to a vinyl chloride resin, so that the light resistance was improved. Although it was observed, the releasability was poor, abnormal transfer occurred, and peeling marks were observed.
In the combination of the thermal transfer sheet and thermal transfer image-receiving sheet obtained in Comparative Example 3, the dye-receiving layer of the thermal transfer image-receiving sheet was obtained by adding only an amino-modified silicone oil to a vinyl chloride resin, thus improving the release property. However, the light resistance was insufficient.
In the combination of the thermal transfer sheet and the thermal transfer image-receiving sheet obtained in Comparative Example 4, since the dye-receiving layer of the thermal transfer image-receiving sheet was a polyester resin as the binder resin, epoxy-modified silicone oil and amino-modified silicone Although it contained oil, the releasability was poor, abnormal transfer occurred, severe peeling marks were observed, and the light resistance was also very poor.
In the combination of the thermal transfer sheet and thermal transfer image-receiving sheet obtained in Comparative Example 5, the dye-receiving layer of the thermal transfer image-receiving sheet was obtained by adding an epoxy-modified silicone oil and a polyether-modified silicone oil to a vinyl chloride resin. Further, the releasability was insufficient, the light resistance was insufficient, and the transferability of the protective layer was deteriorated.

DESCRIPTION OF SYMBOLS 1 Base material 2 Dye layer 3 Back layer 4 Dye primer layer 6 Main protective layer for transferable protective layer 7 Adhesive layer for transferable protective layer 8 Transferable protective layer 10 Thermal transfer sheet 11 Other base material 12 Dye receiving layer 13 Heat insulation layer 20 Thermal transfer image receiving sheet

Claims (6)

A thermal transfer sheet in which a dye layer is provided on one side of the substrate and a back layer is provided on the other side of the substrate, and a thermal transfer image receiving sheet in which a dye receiving layer is provided on one side of the other substrate In combination with
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The combination of a thermal transfer sheet and a thermal transfer image-receiving sheet, wherein the dye-receiving layer of the thermal transfer image-receiving sheet contains a vinyl chloride resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.   The combination of a thermal transfer sheet and a thermal transfer image-receiving sheet according to claim 1, wherein the amino-modified silicone oil in the dye-receiving layer is an amino-modified silicone oil having a diamine in the side chain.   The thermal transfer sheet and thermal transfer image-receiving sheet according to claim 1 or 2, wherein the amino-modified silicone oil in the dye-receiving layer is contained in an amount of 0.5% by mass to 4% by mass with respect to the total solid content of the dye-receiving layer. Combination. A thermal transfer sheet in which a dye layer is provided on one side of the substrate and a back layer is provided on the other side of the substrate, and a thermal transfer image receiving sheet in which a dye receiving layer is provided on one side of the other substrate An image forming method for forming an image on the thermal transfer image-receiving sheet using a combination of
The dye layer of the thermal transfer sheet contains a dye and a binder resin, and one kind is provided on one surface of the base material, or two or more kinds are provided in the surface order,
At least one of the dye layers contains nitrocellulose as the binder resin within a range of 50% by mass to 100% by mass with respect to the total solid content of the binder resin,
The dye-receiving layer of the thermal transfer image-receiving sheet contains an vinyl-modified resin, an epoxy-modified silicone oil, and an amino-modified silicone oil.   The image forming method according to claim 4, wherein the amino-modified silicone oil in the dye-receiving layer is an amino-modified silicone oil having a diamine in a side chain.   The image forming method according to claim 4 or 5, wherein the amino-modified silicone oil in the dye-receiving layer is contained in an amount of 0.5% by mass or more and 4% by mass or less based on the total solid content of the dye-receiving layer.

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