JP2017177749A - Thermal transfer recording material, and method for producing printed object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer recording material capable of obtaining a printed object which has high printing density while excellent in releasability, suppresses bleeding and is excellent in quality and light resistance, and to provide a method for producing a printed object.SOLUTION: In a thermal transfer recording material in combination with a thermal transfer sheet and a thermal transfer image-receiving sheet, the thermal transfer sheet has a first base material, a dye layer that is arranged on one surface of the first base material and contains a dye and a binder resin, and a back face layer arranged on the other surface of the first base material, and contains a phenoxy resin as the binder resin of the dye layer, where the thermal transfer image-receiving sheet has a second base material and a dye receiving layer arranged on one surface of the second base material, and the dye receiving layer is a cured product of a resin composition containing a hydroxyl group-containing thermoplastic resin and a curing agent reacting with a hydroxyl group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet are combined, and a printed material manufacturing method using the thermal transfer sheet and the thermal transfer image receiving sheet.

  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.

  Conventionally, butyral and acetal resins have been known as binder resins used in the dye layer of heat-sensitive sublimation thermal transfer sheets (see Patent Document 1). A dye layer containing a butyral or acetal resin as a binder resin has excellent storage stability, but has a problem that the dye transfer efficiency is low and the printing density may be low.

  In Patent Document 2, as a thermal transfer sheet having high dye transfer efficiency and good storage stability, in a dye layer mainly composed of a thermal transfer dye and a binder resin, the binder resin is composed of a phenoxy resin, A thermal transfer sheet is described in which the weight ratio of the thermal transfer dye to the binder resin weight is specified. However, as will be shown in a comparative example described later, even with a thermal transfer sheet using a phenoxy resin as a binder resin, depending on the thermal transfer image receiving sheet to be combined, the dye transfer efficiency becomes insufficient and the print density becomes insufficient. There was a case.

JP 2009-286060 A JP 2013-146877 A

In recent years, with the increase in speed of printers, the dye receiving layer at the time of printing is given a higher applied energy in a shorter time, and the thermal transfer sheet is peeled off from the dye receiving layer in a high temperature state at a high speed. ing. Therefore, there is a need for a thermal transfer recording material that combines a thermal transfer sheet and a thermal transfer image-receiving sheet, which are likely to cause fusion in high-speed printers and have better releasability. Poor releasability may cause thermal fusion between the dye layer and the dye receiving layer, or may cause peeling marks on the printed matter when the dye layer is peeled off from the dye receiving layer, or may cause poor running. In many cases, the quality of the printed matter is deteriorated due to heat fusion or peeling marks, and there is a problem in the process.
In order to improve releasability, a technique of adding a release agent such as silicone oil to the dye receiving layer is used, and silicone oil is also used in the dye receiving layer described in Patent Document 2. . However, when a release agent is added to improve the releasability, another problem arises that an image blurs with time.
Further, as the speed of the printer increases, it may become difficult to obtain a high density image. In particular, when the thermal transfer image-receiving sheet is a card (ID card, credit card, etc.) using a plastic sheet as a base material, the base material is harder and more expensive than photographic printing paper using a paper base material. It was more difficult to obtain a density image.
Furthermore, it is known that the light fastness of the printed matter is increased by sufficiently diffusing the dye in the dye-receiving layer. However, the amount of heat applied to the dye-receiving layer is reduced by increasing the speed of the printer, and the dye-receiving layer. In some cases, the dye cannot be sufficiently diffused, and it is sometimes difficult to obtain the light resistance of the image as before. When the thermal transfer image receiving sheet is a card (ID card, credit card, etc.), particularly high light resistance is required.

  The present invention has been made in view of the above problems, and has a thermal transfer sheet that is excellent in releasability, has a high printing density, has suppressed bleeding, and has a high quality and excellent light resistance. Providing a thermal transfer recording material combined with a thermal transfer image-receiving sheet, and using the thermal transfer recording material, while having excellent releasability, printing density is high, bleeding is suppressed, and high quality and light resistance are excellent. It is an object of the present invention to provide a method for producing a printed matter.

The thermal transfer recording material according to the present invention is a thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet are combined,
The thermal transfer sheet is disposed on a first substrate, a dye layer containing a dye and a binder resin disposed on one surface of the first substrate, and the other surface of the first substrate. And containing a phenoxy resin as a binder resin of the dye layer,
The thermal transfer image-receiving sheet has a second substrate and a dye-receiving layer disposed on one surface of the second substrate, and the dye-receiving layer includes a hydroxyl group-containing thermoplastic resin, a hydroxyl group, It is the hardened | cured material of the resin composition containing the hardening | curing agent which reacts, It is characterized by the above-mentioned.

The method for producing a printed material according to the present invention includes a first base material, a dye layer containing a dye and a binder resin disposed on one surface of the first base material, and the first base material. A back layer disposed on the other surface, and preparing a thermal transfer sheet containing a phenoxy resin as a binder resin of the dye layer;
A second substrate and a dye-receiving layer disposed on one surface of the second substrate, wherein the dye-receiving layer comprises a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group. A step of preparing a thermal transfer image receiving sheet, which is a cured product of a resin composition comprising:
Superposing the dye layer surface of the thermal transfer sheet and the dye receiving layer surface of the thermal transfer image receiving sheet, thermally transferring the dye onto the dye receiving layer, and forming an image on the thermal transfer image receiving sheet, It is characterized by that.

  In the thermal transfer recording material according to the present invention and the method for producing a printed matter, the hydroxyl group-containing thermoplastic resin is at least one of a polyvinyl butyral resin and a cellulose acetate-based resin. This is preferable from the viewpoint of obtaining a printed matter having excellent light resistance.

  In the method for producing a thermal transfer recording material and a printed material according to the present invention, the thermal transfer image-receiving sheet is a card having a deflection amount of 35 mm or less in a bending strength test defined in JIS X 6305-1: 2010. Even if it exists, it can be used favorably.

  According to the present invention, a thermal transfer recording in which a thermal transfer sheet and a thermal transfer image receiving sheet are combined, which is excellent in releasability, has a high printing density, has suppressed bleeding, and has a high quality and excellent light resistance. Provided are a material and a method for producing a printed matter having high print density, excellent bleeding resistance, high quality, and excellent light resistance, using the thermal transfer recording material, while being excellent in releasability. be able to.

It is sectional drawing which shows typically an example of the thermal transfer recording material which concerns on this invention. It is sectional drawing which shows typically another example of the thermal transfer recording material which concerns on this invention. It is sectional drawing which shows typically another example of the thermal transfer sheet used for the thermal transfer recording material which concerns on this invention. It is sectional drawing which shows typically another example of the thermal transfer image receiving sheet used for the thermal transfer recording material which concerns on 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 as defined in JIS K 6900: 1994. According to the definition in JIS K 6900: 1994, a sheet is thin and generally refers to a flat product whose thickness is small for the length and width, and a film is extremely small compared to the length and width, and the maximum thickness. A thin, flat product of arbitrarily limited length, typically 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 thermal transfer recording material according to the present invention is a thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet are combined,
The thermal transfer sheet is disposed on a first substrate, a dye layer containing a dye and a binder resin disposed on one surface of the first substrate, and the other surface of the first substrate. And containing a phenoxy resin as a binder resin of the dye layer,
The thermal transfer image-receiving sheet has a second substrate and a dye-receiving layer disposed on one surface of the second substrate, and the dye-receiving layer includes a hydroxyl group-containing thermoplastic resin, a hydroxyl group, It is the hardened | cured material of the resin composition containing the hardening | curing agent which reacts, It is characterized by the above-mentioned.

  In the thermal transfer recording material according to the present invention, the curing of the resin composition in which the dye layer contains a phenoxy resin as the binder resin, the curing agent in which the dye receiving layer reacts with a hydroxyl group, and a hydroxyl group-containing thermoplastic resin. By selecting and combining the thermal transfer image-receiving sheet, which is a product, it is possible to obtain a high-quality and light-resistant printed product that has excellent releasability but high print density and suppression of bleeding.

The phenoxy resin contained in the dye layer is a linear polymer synthesized from bisphenols and epichlorohydrin, and has an aromatic ring, hydroxyl group, and ether bond in the main chain, so it has an affinity that is not too strong for the dye. It is. On the other hand, the dye receiving layer, which is a cured product of a resin composition containing a curing agent that reacts with a hydroxyl group and a hydroxyl group-containing thermoplastic resin, is not too polar because the hydroxyl group is consumed by crosslinking, It is easy to accept. Therefore, when heated from the back side of the dye layer containing phenoxy resin as a binder resin, it is presumed that the dye is sufficiently transferred to the dye receiving layer and the printing density is increased.
Further, a cured product of a resin composition containing a curing agent that reacts with a hydroxyl group and a hydroxyl group-containing thermoplastic resin as a binder resin of the dye receiving layer is selected as a thermal transfer sheet in which the dye layer contains a phenoxy resin as the binder resin. Due to the combination, the releasability was improved because the cured product of the resin composition containing a curing agent that reacts with a hydroxyl group and a hydroxyl group-containing thermoplastic resin consumes the hydroxyl group due to crosslinking, resulting in a three-dimensional network structure. This is presumed to be because the surface hardness is high and the compatibility with the phenoxy resin is low. Accordingly, it is presumed that the dye layer containing the phenoxy resin as the binder resin and the dye receiving layer are easily peeled off without being thermally fused at the time of dye transfer, and abnormal transfer can be suppressed. In addition, by selecting a cured product of a resin composition containing a curing agent that reacts with a hydroxyl group and a hydroxyl group-containing thermoplastic resin as a binder resin for the dye-receiving layer, a mold release that generates bleeding such as silicone oil in the dye-receiving layer. Since sufficient releasability can be ensured even if no agent is contained, bleeding can be suppressed.
In addition, since the dye receiving layer, which is a cured product of a resin composition containing a curing agent that reacts with a hydroxyl group and a hydroxyl group-containing thermoplastic resin, has a polarity close to that of the dye, the dye molecule after dye transfer is deep in the dye receiving layer. It is estimated that the distance between the dye molecules can be increased, the interaction between the dye molecules can be suppressed, and the light resistance of the dye can be improved.

Hereinafter, the thermal transfer recording material of the present invention, and the thermal transfer sheet and thermal transfer image receiving sheet used in the method for producing a printed matter of the present invention will be specifically described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of the thermal transfer recording material of the present invention, FIG. 2 is a schematic sectional view showing another example of the thermal transfer recording material of the present invention, and the thermal transfer recording material 1 of the present invention is The thermal transfer sheet 10 shown in the upper diagram and the thermal transfer image receiving sheet 20 shown in the lower diagram are combined.
As shown in FIG. 1, a thermal transfer sheet 10 used in the present invention includes a first substrate 2, a dye layer 3 disposed on one surface of the first substrate 2, and the first substrate 2. The structure which has the back surface layer 4 arrange | positioned at the other surface of the base material 2 is taken. In the present invention, the dye layer 3 contains a dye and a binder resin, and the binder resin contains a phenoxy resin. In the thermal transfer sheet 10 used in the present invention, a dye primer layer 5 may be disposed between the first substrate 2 and the dye layer 3 as shown in FIG. Further, a back primer layer (not shown) may be disposed between the first substrate 2 and the back layer 4.
Further, the thermal transfer image receiving sheet 20 used in the present invention in FIG. 1 has a configuration having a second substrate 11 and a dye receiving layer 12 disposed on one surface of the second substrate 11. As shown in FIG. 2, an intermediate layer 13 may be further disposed between the second base material 11 and the dye receiving layer 12. The back surface layer 14 can also be provided on a surface different from the surface on which the dye receiving layer 12 of the second substrate 11 is disposed.
Hereinafter, the configuration of the thermal transfer sheet 10 and the thermal transfer image receiving sheet 20 constituting the thermal transfer recording material 1 will be described in detail.

≪Thermal transfer sheet≫
(First base material)
The first substrate 2 used in the thermal transfer sheet 10 of the present invention is an essential configuration in the thermal transfer sheet 10 of the present invention, and is provided to hold the dye layer 3 and the back layer 4. The material of the first substrate 2 is not particularly limited, but has the mechanical characteristics that can withstand the heat applied by the thermal head when the dye of the dye layer 3 is transferred onto the thermal transfer image-receiving sheet and has no trouble in handling. Is desirable. 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.

  The thickness of the first substrate 2 can be appropriately set according to the material so that the strength and heat resistance thereof are appropriate, and is generally 2.5 μm or more and 100 μm or less, preferably 1 μm or more. 10 μm or less. If the substrate sheet is too thick, the mechanical strength is high, but the transfer of thermal energy is insufficient when transferring dye from the dye layer of the thermal transfer sheet to the dye-receiving layer of the thermal transfer image-receiving sheet, resulting in poor transferability. Tend to. On the other hand, if the thickness of the base sheet is too thin, the mechanical strength may be insufficient and the dye layer or the like may not be supported. In addition, the base sheet may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment on the surface in advance.

(Dye layer)
The dye layer 3 of the present invention is a layer formed by supporting a dye with a binder resin. In the form shown in FIG. 1, one type of (single) dye layer 3 is provided on one surface of the first substrate 2, but as shown in FIG. 3, two or more types are used. It is also possible to repeatedly provide the same dye layer on the same surface of the first base material 2 in the surface order (for example, Y (yellow) dye layer, M (magenta) dye layer, C (cyan) dye layer in FIG. 3). ). Moreover, it is good also as providing a transferable protective layer on the same surface of the 1st base material 2 (for example, OP layer of FIG. 3). The dye layer used in the present invention contains a phenoxy resin as the binder resin.

<Dye>
As the dye material contained in the dye layer 3, 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 3 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 3, a binder resin for holding the dye is used together with the dye. The dye layer used in the present invention contains a phenoxy resin as a binder resin.
It is preferable that the phenoxy resin is contained 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, and further the phenoxy resin is contained within the range of 70% by mass or more and 100% by mass or less. It is preferable that the resin further contains a phenoxy resin within the range of 90% by mass or more and 100% by mass or less, and particularly 100% by mass of the phenoxy resin is contained with respect to the total solid content of the binder resin. It is preferable.

[Phenoxy resin]
The phenoxy resin is a high molecular weight polyhydroxy polyether (thermoplastic resin) synthesized from the reaction of bisphenols and epichlorohydrins.
Bisphenols are compounds having two hydroxyphenyl groups.
Two hydroxyphenyl groups may further have a substituent such as an alkyl group or a halogen atom. In addition, examples of the bisphenols used include structures in which two hydroxyphenyl groups are linked by various divalent linking groups X.

Examples of the divalent linking group X include a divalent hydrocarbon group that may be substituted with a halogen atom, —O—, —S—, —SO—, and —SO ₂ —. Examples of the divalent hydrocarbon group include a chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.

  Examples of the phenoxy resin used in the present invention include a resin having a structural unit represented by the following general formula (1).

(In the general formula (1), X represents the divalent linking group X, and Y ₁ and Y ₂ each independently represent a substituent. K 1 and k ₂ are each independently a number of 0 or more and 4 or less. is there.)

Examples of the bisphenol used include bis (4-hydroxyphenyl) diphenylmethane (bisphenol BP), bis (4-hydroxyphenyl) phenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP). ), 1,1-bis (4-hydroxyphenyl) 1-phenylpropane 1,1-bis (4-hydroxyphenyl) 1-phenylbutanebis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane (bisphenol B), 2,2- Bis (4-hydroxy-3-methylphenyl) propa (Bisphenol C), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as -hydroxy-3-isopropylphenyl) propane (bisphenol G); 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane ( Bis (hydroxyaryl) cycloalkanes such as bisphenol Z); Dihydroxydiaryl ethers such as 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis (4-hydro Dihydroxydiarylfluorenes such as cis-3-methylphenyl) fluorene; dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; -Dihydroxydiaryl sulfoxides such as dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone = bis (4-hydroxyphenyl) sulfone (bisphenol S), 4 , 4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and the like.
Among them, from the viewpoint of releasability, the bisphenol is one or more selected from the group consisting of bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxydiaryl ethers, and dihydroxydiarylfluorenes. It is preferable that there are bis (hydroxyaryl) alkanes and bis (hydroxyaryl) cycloalkanes.

  Examples of epichlorohydrins and the like include epichlorohydrin, epibromohydrin, 1,2-epoxy-1-methyl-3-chloropropane, 1,2-epoxy-1-butyl-3-chloropropane, and the like. Can be mentioned.

The phenoxy resin is obtained by adding about 1 mol of dihydric phenol and alkali such as NaOH or KOH to 0.6 mol to 1.5 mol per 1 mol of epichlorohydrin, and mixing them at a temperature of about 40 ° C. be able to. The polymer preferably has a weight average molecular weight of 10,000 or more and 100,000 or less, more preferably 15,000 or more and 45,000 or less.
In addition, the weight average molecular weight in this invention says the polystyrene conversion weight average molecular weight by GPC.

  Moreover, butyl glycidyl ether, higher fatty acid glycidyl ester, etc. can be added and used as a modifying agent as a reactive diluent instead of epichlorohydrin.

  Moreover, it is also possible to modify by introducing a side chain by reacting with a hydroxyl group in the phenoxy resin. The substance to be reacted can be grafted by an ester bond with an acid anhydride such as succinic anhydride, maleic anhydride, or trimellitic anhydride. Alternatively, esterification with fatty acids is also possible. Triethylenediamine or the like can be used as a catalyst. The preferred grafting rate depends on the compound to be grafted, but is preferably 10% or more and 50% or less, particularly preferably 25% or more and 30% or less.

  As the phenoxy resin used in the present invention, commercially available products can be used as appropriate. , YP-70 (Nippon Steel & Sumikin Chemical) and the like.

[Other binder resins]
The binder resin for the dye layer may contain only a phenoxy resin, and other binder resins may be contained together with the phenoxy resin as long as the effects of the present invention are not impaired.

  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 3 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 3 may contain other release agents within a range that does not interfere with 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 3 is not particularly limited, and a dye, a binder resin containing a phenoxy resin, and additives as necessary, for example, a mold release agent or inorganic fine particles, 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 3 shall be 0.35 g / m < ² > or less at the time of drying. By making the coating amount of the dye layer 3 within this range, the dye transfer efficiency at the time of transfer can be improved, and the dye contained in the dye layer 3 can be transferred onto the thermal transfer image receiving sheet without waste, In addition, the storage stability requirement can be satisfied. In addition, when the coating amount of the dye layer 3 exceeds 0.35 g / m ² at the time of drying, the dye transfer efficiency may be lowered. The lower limit of the dye layer 3 is not particularly limited, but when the coating amount of the dye layer is less than 0.25 g / m ² at the time of drying, the blending ratio of the sublimable dye to the phenoxy resin may be increased. In some cases, sufficient print density cannot be obtained. Therefore, in consideration of this point, the coating amount of the dye layer is preferably 0.25 g / m ² or more and 0.35 g / m ² or less at the time of drying.

When the content of the dye contained in the dye layer 3 is small, a sufficient print density may not be obtained. In consideration of this point, in the dye layer, the mass ratio of the dye and the binder resin contained therein (D / B ratio (dye / binder resin)) can provide a printed matter having a sufficient print density. Therefore, it is preferably 2.5 or more.
On the other hand, if the mass ratio of the dye to the binder resin (D / B ratio (dye / binder resin)) is too large, the amount of the dye with respect to the binder resin will be too large, and the binder will not be able to hold the dye and storage stability will be maintained. May decrease. Therefore, considering this point, the D / B ratio is preferably in the range of 4 or less, and more preferably in the range of 2.5 or more and 3.5 or less.

(Back layer)
As shown in FIG. 1, a back layer 4 is disposed on the other surface of the first base member 2 to improve heat resistance, running performance of the thermal head during printing, and the like.

  The back layer 4 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. For example, it is preferable to combine a curing agent that reacts with a hydroxyl group, such as a polyisocyanate resin, with a hydroxyl group-containing thermoplastic resin having a hydroxyl group among the thermoplastic resins.
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 4 has a mold release agent such as wax, higher fatty acid amide, phosphoric ester compound, metal soap, silicone oil, surfactant, fluorine, etc. 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 4 is formed, for example, by applying a coating liquid obtained by dispersing or dissolving the thermoplastic resin and various additives added as necessary in an appropriate solvent, on the opposite side of the dye layer 3 of the first base 2. On this surface, 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 4 is preferably 3 g / m ² or less after drying, from the viewpoint of improvement in heat resistance or the like, and is 0.1 g / m ² or more and 2 g / m ² or less. It is more preferable.

(Transferable protective layer)
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.

  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, and ionizing radiation curable resins. Examples thereof include ultraviolet blocking resins.

  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 transfer protective layer having a single-layer structure or the transfer protective layer having a multilayer structure usually has a thickness of 0.5 μm or more and 10 μm or less, depending on the type of the protective layer forming resin. Preferably there is.

  An adhesive layer may be disposed on the outermost surface of the transferable protective layer. The adhesive layer is formed of a resin having good adhesiveness when heated, such as an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride / vinyl acetate copolymer resin, a polyester resin, and a polyamide resin. be able to. The thickness of the adhesive layer is usually 0.1 μm or more and 5 μm or less.

In the thermal transfer sheet 1 used in the present invention, a known configuration conventionally provided in a sublimation thermal transfer sheet may be further arranged.
For example, it is preferable that the dye primer layer 5 is disposed between the first substrate 2 and the dye layer 3. By providing the dye primer layer 5, the printing density can be improved. As the dye primer layer, conventionally known ones can be appropriately selected and used. For example, polyvinyl pyrrolidone, alumina sol and the like are preferably used.

≪Thermal transfer image receiving sheet≫
(Second base material)
The second substrate used in the thermal transfer image-receiving sheet of the present invention has a function of holding a dye-receiving layer, but since heat is applied during thermal transfer, it is a machine that does not hinder handling even in a heated state. It is preferable to have a mechanical strength. The material of the second base material is not particularly limited, and for example, condenser paper, glassine paper, sulfuric acid paper, synthetic paper (polyolefin type, polystyrene type, etc.), high quality paper, art paper, coat Paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, silver salt photograph with cellulose coated on both sides Resin coated paper used as a base material for printing paper, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, poly Vinyl chloride, polyvinylidene chloride Of various plastic films or sheets can be used, also white pigment, these synthetic resins, formed by adding a filler, a film (porous film) having fine voids (microvoids) inside the substrate can also be used.
The second substrate may be a single layer or a laminate of two or more layers. Examples thereof include a multilayer laminated sheet obtained by laminating two or more kinds of the above sheets by a known method such as a dry laminating method, a wet laminating method, or a melt laminating method.
When the adhesion of the second base material to the layer formed on the surface is poor, it is preferable to subject the surface to easy adhesion treatment such as various primer treatments and corona discharge treatment.

  The size and thickness of the second base material are not particularly limited and can be appropriately selected according to the purpose of use of the thermal transfer image-receiving sheet. Examples of standardized sizes include postcard size, card size, and business card. There are size etc. The thickness is appropriately selected in the range of usually 50 μm or more and 800 μm or less.

In the thermal transfer image receiving sheet of the present invention, a card base material used as a base material for cards can be suitably used as the second base material. As a card substrate, when a thermal transfer image-receiving sheet having a dye-receiving layer is disposed, a card base that becomes a card having a bending amount in a bending strength test defined in JIS X 6305-1: 2010 of 35 mm or less It is preferable to select a material.
The bending amount in the bending strength test specified in JIS X 6305-1 is in accordance with the standard of JIS X 6322-1: 2001 (JIS X 6301: 2005 8.1 “Static Bending Strength”). According to the test method of 6305-1: 2010 5.7., It can obtain by measuring the deflection amount (h1-h2) as follows.
B) Hold the short side 3 mm on one side of the card and record the height h1 (mm) from the reference surface of the reverse side.
B) A load of 0.7 N is applied to the reverse side short side of 3 mm, and the height h2 (mm) from the reference surface of the reverse side short side is recorded for 1 minute.
C) Remove the load, and after 1 minute, record the height h3 (mm) from the reference surface of the reverse short side.
D) Record the deflection amount (h1-h2) (mm) and the deformation amount (h1-h3) (mm).
Used equipment:
Metal straight scale TZ-RS15
Metal straight scale TZ-RS60
Stopwatch S056-4000
Thermo-Hygrometer T & D TR-72U
Electronic non-automatic scale EK-1200i made by A & D Co., Ltd.

Among them, in the present invention, for example, a card base material having an information recording function in which a magnetic layer, an optical recording layer, an IC chip and the like are incorporated can be suitably used.
When the thermal transfer image-receiving sheet is a card (such as an ID card or a credit card), the cushioning property of the image-receiving layer is often insufficient compared to a photographic printing paper using a paper base material. And the problem of image bleeding tends to occur more remarkably because the dye tends to accumulate at a high concentration near the outermost surface of the image receiving layer. Further, cards are likely to be exposed to high temperature conditions, and the problem of blurring of images tends to occur more remarkably. Further, the cards need to be easily exposed to the outdoors or light and have high light resistance. Therefore, when the thermal transfer image-receiving sheet of the present invention is a card, that is, when a card substrate is used as the second substrate, the effects of the present invention are more remarkably exhibited.

  As another example of the thermal transfer image receiving sheet used in the thermal transfer recording material according to the present invention, FIG. 4 shows a thermal transfer image receiving sheet when the second base material is an IC card. FIG. 4 is a schematic cross-sectional view of an IC card 30 provided with a second base material 21, a dye receiving layer 22 and an intermediate layer 23. The second substrate 21 includes an IC module having a predetermined thickness between the first substrate sheet member 25 and the second substrate sheet member 25 ′. The IC module includes an antenna body 28, an IC chip 29, a reinforcing plate 31, and the like, and these are provided in the inlet 27. In addition, the second base material 21 includes an inlet 27 disposed between the first base material sheet member 25 and the second base material sheet member 25 ′, and laminates the members with the adhesives 26 and 26 ′ interposed therebetween. This is a laminated structure.

  The card substrate can be formed, for example, by bonding the second substrate sheet member to the first substrate sheet member with an adhesive using a known method as appropriate. In addition, by embedding an electronic component composed of an IC chip that electrically stores user information and a coiled antenna body connected to the IC chip in an adhesive, a card substrate with an IC chip can be obtained. Can be formed. You may form a card | curd base material by bonding the 2nd base material sheet member with an adhesive agent, after providing the dye receiving layer mentioned later on the one surface side of a 1st base material sheet member.

  As a base sheet member for forming a card base, a resin sheet such as polyethylene terephthalate (PET), PET-G, polyethylene naphthalate (PEN), vinyl chloride, polycarbonate, triacetyl cellulose, acrylic, etc. is preferably used. However, PET, PET-G, or PEN is preferable from the viewpoints of mechanical strength, dimensional stability, and solvent resistance. Among these, PET or PET-G is particularly preferable from the viewpoints of transparency, processability, and cost.

When an adhesive is used for bonding to form a card substrate, a conventionally known adhesive can be used without any particular limitation. In the present invention, a hot melt adhesive or the like is preferably used. Examples thereof include ethylene-vinyl acetate copolymer (EVA) -based, polyester-based, polyamide-based, thermoplastic elastomer-based, and polyolefin-based adhesives. Among these, a moisture curable adhesive is preferable. In addition to the above, the adhesives disclosed in JP 2000-036026 A, JP 2000-21278 A, JP 2000-218555 and the like are preferably used as the moisture curable adhesive. Can do. In addition, when bonding each member using an adhesive agent, the total thickness of the adhesive layer and the electronic component layer (inlet thickness) is preferably 100 μm or more and 600 μm or less, more preferably 150 μm or more and 500 μm or less, Particularly preferably, it is 150 μm or more and 450 μm or less.
As a method for forming a predetermined card size, a punching method, a cutting method, or the like can be mainly employed.

(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 a cured product of a resin composition containing a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with the hydroxyl group.
Since the dye-receiving layer is a cured product of a resin composition containing a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group, even if combined with a thermal transfer sheet provided with a dye layer containing a phenoxy resin, While having excellent releasability, the dye acceptability is also high, a printed matter having a high printing density can be obtained, and the light resistance of the printed matter can be improved.
Since the dye receiving layer is a cured product of a resin composition containing a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group, the reaction of reacting with the hydroxyl group of the thermoplastic resin and the hydroxyl group of the curing agent. It includes a cross-linked structure in which a hydroxyl group of a hydroxyl group-containing thermoplastic resin and a curing agent are bonded to each other to form a three-dimensional network structure.

<Hydroxyl-containing thermoplastic resin>
The hydroxyl group-containing thermoplastic resin used in the present invention is a thermoplastic resin containing a hydroxyl group bonded to a hydrocarbon group. The hydroxyl group here means a hydroxyl group bonded to a hydrocarbon group, for example, OH contained in a carboxyl group (—COOH) is excluded. Typically, it is preferably an alcoholic hydroxyl group which is a hydroxyl group bonded to a hydrocarbon group and is a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group).

  Examples of the hydroxyl group-containing thermoplastic resin used in the present invention include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, acetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and nitrified cotton. Vinyl resins such as polyvinyl alcohol, polyvinyl acetal resins such as polyvinyl butyral resin and polyacetoacetal resin, acrylic resins such as polyacrylate resin and styrene acrylate resin, polyamideimide resin, polyurethane resin, silicone Examples thereof include modified or fluorinated urethane resins.

As the hydroxyl group-containing thermoplastic resin used in the present invention, the number average molecular weight is preferably 10,000 or more, more preferably 30000 or more, from the viewpoint of releasability.
Here, the number average molecular weight refers to the number average molecular weight converted to polystyrene by GPC.

  The hydroxyl group-containing thermoplastic resin used in the present invention has a high hydroxyl group value because it has a high print density and is excellent in releasability while being excellent in releasability. It is preferably 1 mgKOH / g or more, while it is preferably 100 mgKOH / g or less. Here, the hydroxyl value represents the number of mg of potassium hydroxide required to acetylate the hydroxyl group contained in 1 g of the solid content of the hydroxyl group-containing thermoplastic resin, and is measured by the method described in JIS K 0070: 1992. Value.

In addition, as the hydroxyl group-containing thermoplastic resin used in the present invention, it is possible to obtain a high-quality and light-resistant printed material, which has excellent releasability, high printing density, and suppressed bleeding. The transition temperature (Tg) is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. On the other hand, the glass transition temperature (Tg) is preferably 100 ° C. or less, more preferably 90 ° C. or less, because the printing density may be lowered if the glass transition temperature (Tg) is too high. .
In addition, the glass transition temperature (Tg) in this invention is a temperature calculated | required based on the measurement (DSC method) of the calorie | heat amount change by DSC (differential scanning calorimetry).

  In addition, as the hydroxyl group-containing thermoplastic resin used in the present invention, a resin having a solubility parameter (SP value) far from that of the phenoxy resin used in the dye layer is selected from the viewpoint of improving releasability. It is preferable to do. If the compatibility or solubility of each binder resin used in the dye layer and the dye receiving layer is low, the affinity between the binder resins will be low, and the adhesion at the interface will become unstable, and the contact between the two substances It is estimated that it works to reduce the area and the releasability is improved.

  As the hydroxyl group-containing thermoplastic resin, among them, polyvinyl acetal resins such as polyvinyl butyral resin and polyacetoacetal resin having a moderate hydroxyl group in the molecule, and cellulose resins are preferably used. Among them, at least one of polyvinyl butyral resin and cellulose acetate-based resin is preferably used from the viewpoint of releasability, and among them, polyvinyl butyral resin and cellulose acetate butyrate are preferable from the viewpoint of releasability and light resistance. At least one is preferably used. In particular, the presence of bulky groups such as butyral groups and butyrate groups in the polymer in a high proportion makes the surface of the image-receiving layer hydrophobic, and the synergistic effect of these improves the releasability and dye dispersibility. It is estimated that.

In the polyvinyl butyral resin, it is excellent in printability, has good releasability from the thermal transfer sheet, and can form an image excellent in light resistance. The structural unit is preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 40 mol% or less.
In cellulose acetate butyrate, those having a hydroxyl group ratio of 0.1% to 5% are preferably used.

In addition, the hydroxyl group containing thermoplastic resin used for this invention may be only one type, or may be two or more types.
The content of the hydroxyl group-containing thermoplastic resin is preferably from 80% by mass to 98% by mass (solid content conversion), more preferably from 85% by mass to 95% by mass, based on the total dye receiving layer material. In the present invention, the “solid content” means all components other than the solvent.

<Hardening agent that reacts with hydroxyl group>
The curing agent that reacts with a hydroxyl group used in the present invention crosslinks the hydroxyl group-containing thermoplastic resin using the hydroxyl group. As a hardening | curing agent which reacts with the hydroxyl group used by this invention, an epoxy compound, a methylol compound, an isocyanate compound etc. are mentioned, for example. In the present invention, a polyisocyanate compound is preferably used as the curing agent to be combined with the hydroxyl group-containing thermoplastic resin.

  The polyisocyanate compound used as the curing agent can be appropriately used as long as it has two or more isocyanate groups in the molecule. Examples thereof include at least one of aromatic polyisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and derivatives thereof. Here, the araliphatic polyisocyanate refers to a polyisocyanate having a structure in which an isocyanate group is bonded to an aromatic ring via an aliphatic carbon atom.

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, p-phenylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate and the like can be mentioned.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, bis (isocyanatomethyl) norbornane, and the like.
Examples of the araliphatic polyisocyanate include xylylene diisocyanate, tetramethylxylylene diisocyanate, and ω, ω′-diisocyanate-1,4-diethylbenzene.
Examples of the polyisocyanate compound derivatives include multimers such as isocyanurates of the polyisocyanate compounds, multimers such as trimers, dimers and pentamers, and polyols such as the polyisocyanate compounds and trimethylolpropane. Examples thereof include adducts obtained by reacting with compounds, and modified polyisocyanates such as allophanates and burettes.

  In the present invention, from the viewpoint of light resistance, it is preferable to have a structure in which the nitrogen atom of the isocyanate group is bonded to an aliphatic carbon atom. Aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and these At least one of the derivatives is preferably used. Among these, from the viewpoint of light resistance and releasability, isocyanurates of the above aliphatic polyisocyanates, xylylene diisocyanate, and modified polyisocyanates thereof are preferably used.

  In the dye-receiving layer of the present invention, in particular, the molar ratio (NCO / OH) of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the hydroxyl group-containing thermoplastic resin is 0.01 or more from the viewpoint of releasability and concentration. It is preferable to use a combination of a hydroxyl group-containing thermoplastic resin and a polyisocyanate compound so that it is 5 or less and further 0.5 or more and 3 or less.

In addition, the curing agent that reacts with the hydroxyl group used in the present invention may be only one type or two or more types.
The content of the curing agent that reacts with the hydroxyl group is preferably 2% by mass or more and 20% by mass or less (solid content conversion), and more preferably 5% by mass or more and 10% by mass or less, based on the total dye receiving layer material.

  It can be confirmed that the dye receiving layer is a cured product of a resin composition containing a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group by collecting and analyzing the material from the dye receiving layer. . As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a combination thereof can be applied.

<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.
In the dye-receiving layer of the present invention, it is preferable not to contain a release agent such as silicone oil from the viewpoint of suppressing bleeding, but it may be used as long as it does not interfere with the effects of the present invention. This does not preclude the use of a release agent. Examples of such a release agent include solid waxes such as silicone oil, polyethylene wax, amide wax, Teflon (registered trademark) powder, fluorine-based or phosphate-based surfactant, and the like.
Moreover, you may use together binder resin other than a hydroxyl-containing thermoplastic resin in the range which does not inhibit the effect of this invention. Examples of such a binder resin include acrylic resins, polyester resins, urethane resins, and vinyl chloride resins that do not correspond to a hydroxyl group-containing thermoplastic resin. Even when a binder resin other than the hydroxyl group-containing thermoplastic resin is used in combination, the hydroxyl group-containing thermoplastic resin is the main component of the binder resin, that is, 50% by mass or more of the total of the binder resin. The total content 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 g / m ² or more and 10 g / m ² or less in a dry state.

(Middle layer)
An intermediate layer 13 may be disposed between the second substrate 11 and the dye receiving layer 12.
The intermediate layer can prevent, for example, the heat applied from the thermal head to the dye-receiving layer 12 from being transferred to the second substrate 11 and the like, and the printing density from being lost. Further, the intermediate layer improves the cushioning property, makes it possible to obtain a printed matter having a low density, a high density and excellent light resistance.
The intermediate layer may have a multilayer structure in which two or more layers are laminated, and is intended to provide adhesion between the heat insulating layer and the image receiving layer, whiteness, concealment, antistatic property, and anti-curl property. It may be a thing.
As the intermediate layer, for example, any conventionally known materials referred to as “heat insulating layer”, “hollow layer”, “hollow particle layer”, and “cushion layer” can be appropriately selected and used.

As an intermediate | middle layer, the heat insulation layer, intermediate | middle layer, etc. of Unexamined-Japanese-Patent No. 2015-066781 Paragraph 0072-0081 are mentioned, for example.
Further, when used in a card substrate, as described in paragraphs 0017 to 0023 of JP 2013-28069 A, dispersed in water such as a styrene acrylic acid copolymer resin and / or gelatin in hollow particles. Preferable examples include a cushion layer obtained by curing a soluble binder resin with a hardener, and an actinic ray cured layer described in paragraphs 0027 to 0056 of JP-A-2014-193421.

The thickness or the coating amount of the intermediate layer is not particularly limited as long as it is appropriately selected according to the purpose. The thickness of the intermediate layer is generally 0.5μm or 10μm or less, the coating amount of the intermediate layer, 0.5 g / ^{m 2} or more 5 g / ^{m 2} or less is preferable in the dry state.

Further, a back layer 14 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 second substrate 11 is disposed.
The thermal transfer image-receiving sheet 20 used in the present invention is not limited to any other various functional layers. These back layer 14 and various functional layers may be provided by appropriately selecting conventionally known layers.

(Method for producing printed matter)
The method for producing a printed material according to the present invention includes a first base material, a dye layer containing a dye and a binder resin disposed on one surface of the first base material, and the first base material. A back layer disposed on the other surface, and preparing a thermal transfer sheet containing a phenoxy resin as a binder resin of the dye layer;
A second substrate and a dye-receiving layer disposed on one surface of the second substrate, wherein the dye-receiving layer comprises a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group. A step of preparing a thermal transfer image receiving sheet, which is a cured product of a resin composition comprising:
Superposing the dye layer surface of the thermal transfer sheet and the dye receiving layer surface of the thermal transfer image receiving sheet, thermally transferring the dye onto the dye receiving layer, and forming an image on the thermal transfer image receiving sheet. It is characterized by.

  That is, the method for producing a printed material according to the present invention includes the thermal transfer sheet 10 having the specific dye layer described in the thermal transfer recording material of the present invention, and the thermal transfer image receiving sheet 20 having the specific dye receiving layer. The dye layer 3 of the thermal transfer sheet 10 described above and the dye receiving layer 12 of the thermal transfer image receiving sheet 20 are overlapped with each other, and the thermal transfer sheet 10 is heated by a thermal head. Image formation is performed by applying heat from the back layer 4 side and transferring the dye contained in the dye layer 3 to the dye receiving layer 12.

In the method for producing a printed matter according to the present invention, a resin composition in which a dye layer contains a phenoxy resin as the binder resin, a curing agent in which the dye receiving layer reacts with a hydroxyl group, and a hydroxyl group-containing thermoplastic resin By selecting and combining with a thermal transfer image-receiving sheet that is a cured product of the above, it is possible to produce a high-quality and light-resistant printed material with high print density and low bleeding while having excellent releasability. can do.
The thermal transfer sheet and thermal transfer image-receiving sheet used in the method for producing a printed product of the present invention are as described in the above-described thermal transfer recording material of the present invention, and detailed description thereof is omitted here.

In the method for producing a printed material according to the present invention, the energy applied from the first substrate side of the thermal transfer sheet by the thermal head may be appropriately adjusted according to the image, and is not particularly limited. In a high-speed printer, for example, an output of 0.25 W (watt) / dot or less, a line speed of 0.5 ms (milliseconds) / L (line) to 5 ms / L, a dot density of 200 dpi (dots per inch) to 600 dpi, Preferably, the output is 0.20 W / dot or less, the line speed is 0.5 ms / L or more and 2 ms / L or less, and the dot density is 200 dpi or more and 400 dpi or less.
According to the method for producing a printed material according to the present invention, since the specific thermal transfer sheet and the specific thermal transfer image receiving sheet described above are used, high density printing can be realized even in the high-speed printing as described above. .

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
A thermal transfer sheet and a thermal transfer image receiving sheet were produced as described below, and a thermal transfer recording material in which the thermal transfer sheet and the thermal transfer image receiving sheet were combined was obtained.
(1) Preparation of thermal transfer sheet A polyethylene terephthalate film having a thickness of 4.5 μm was used as the first base material, and a coating solution for the back layer having the following composition was applied thereon to a dry amount of 0.5 g / m ^2. And dried to form a back layer. Next, on the surface opposite to the side on which the back layer of the first base material is provided, the dye layer coating solution 1 having the following composition is dried so that the dye layer is 0.6 g / m ² when dried. The thermal transfer sheet of Example 1 as shown in FIG. 1 was obtained by applying the coating layer repeatedly in order and then drying to form a dye layer.

<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) Purified Sakai Chemical Industry Co., Ltd.) 10 parts Zinc stearate (SZ-PF Sakai Chemical Industry Co., Ltd.) 10 parts
・ Polyethylene wax (Polywax 3000, manufactured by Toyo Petrolite Co., Ltd.) 10 parts ・ Methyl ethyl ketone 200 parts ・ Toluene 100 parts

<Dye layer coating solution 1>
-Dye represented by the following chemical formula (A) 2.0 parts-Dye (disperse thread 60) 2.0 parts-Dye (dispers violet 26) 3.0 parts-Phenoxy resin (bisphenol A type phenoxy resin, product name: (PKHC, manufactured by InChem) 2.8 parts (solid content)
・ Solvent (methyl ethyl ketone / toluene = 1: 1 solution) 100 parts

(2) Preparation of thermal transfer image-receiving sheet (IC card with dye-receiving layer) On substrate sheet (U2L92W-188, manufactured by Teijin DuPont Films), the dye-receiving layer coating solution 1 is 4 g / m ^2. It was applied to form a coating film to obtain a sheet with a dye receiving layer.
An IC component and another sheet (U2L92W-188) are bonded to the base sheet side of the obtained sheet with the dye-receiving layer via a hot melt adhesive (Macroplast QR3460, manufactured by Henkel), and a roll cutter is used. Then, an IC card with a dye-receiving layer having a thickness of 790 μm and a card size of 55 mm × 85 mm was produced. The IC card had a deflection amount of 20 mm in a bending strength test defined in JIS X6305-1: 2010.

<Dye-receiving layer coating solution 1>
Polyvinyl butyral resin (S-REC BL-1, manufactured by Sekisui Chemical Co., Ltd., vinyl alcohol-derived structural unit is 36 mol%, number average molecular weight 19000) 9 parts Polyisocyanate (Takenate D-110N, trimethylolpropane of xylylene diisocyanate Adduct body, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 part / solvent (methyl ethyl ketone / toluene = 1: 1 solution) 90 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 thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Dye-receiving layer coating solution 2>
Polyvinyl butyral resin (S-REC BH-S, manufactured by Sekisui Chemical Co., Ltd., vinyl alcohol-derived structural unit is 22 mol%, number average molecular weight 66000) 9 parts Polyisocyanate (Takenate D-110N, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 Parts / solvent (methyl ethyl ketone / toluene = 1: 1 solution) 90 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 thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Dye-receiving layer coating solution 3>
Cellulose acetate butyrate (CAB) (CAB-551-0.01, manufactured by EASTMAN CHEMICAL, hydroxyl group 1.5%, number average molecular weight 16000) 9 parts Polyisocyanate (Takenate D-110N, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 Parts / solvent (methyl ethyl ketone / toluene = 1: 1 solution) 90 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 thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Dye-receiving layer coating solution 4>
Polyvinyl butyral resin (S-Rec BL-1, manufactured by Sekisui Chemical Co., Ltd.) 9 parts Polyisocyanate (coronate HX, hexamethylene diisocyanate trimer, 3 isocyanate groups in one molecule, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 part・ Solvent (methyl ethyl ketone / toluene = 1: 1 solution) 90 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 thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Comparative dye receiving layer coating solution 1>
・ Styrene maleic acid resin (X-220, manufactured by Starlight PMC, no alcoholic hydroxyl group) 9 parts ・ Polyisocyanate (Takenate D-110N, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 part ・ Solvent (Methyl ethyl ketone / toluene = 1: 1 solution) 90 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 thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Comparative dye receiving layer coating solution 2>
・ Vinyl chloride resin (vinyl chloride-vinyl acetate copolymer resin, sorbine C, Nissin Chemical Industry Co., Ltd., alcohol-free hydroxyl group-free) 20 parts ・ Carboxyl-modified silicone oil (X-22-3701E, Shin-Etsu Chemical Co., Ltd.) )) 1 part Solvent (methyl ethyl ketone / toluene = 1: 1 solution) 79 parts

(Comparative Example 3)
In Example 1, the thermal transfer sheet of Comparative Example 3 was prepared in the same manner as in Example 1 except that the thermal transfer sheet was formed using the comparative dye layer coating liquid 1 having the following composition for the dye layer coating liquid. And a thermal transfer recording material in which the thermal transfer image-receiving sheet was combined.

<Coating solution 1 for comparative dye layer>
-2.0 parts of the dye represented by the following chemical formula (A)-2.0 parts of the dye (Disper Thread 60)-3.0 parts of the dye (Disperse Violet 26)-Polyvinyl acetal resin (ESREC KS-10, Sekisui Chemical Co., Ltd.) 2.8 parts (solid content)
・ Solvent (methyl ethyl ketone / toluene = 1: 1 solution) 100 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 3 having the following composition in Example 1 for the dye-receiving layer coating solution. A thermal transfer recording material in which a thermal transfer sheet and a thermal transfer image receiving sheet were combined was obtained.
<Comparative dye receiving layer coating solution 3>
・ Polyvinyl butyral resin (ESREC BL-1, manufactured by Sekisui Chemical Co., Ltd.) 10 parts ・ Solvent (methyl ethyl ketone / toluene = 1: 1 solution) 90 parts

[Evaluation]
The thermal transfer recording material obtained by combining the thermal transfer sheet and the thermal transfer image receiving sheet produced in each example and comparative example was evaluated as follows. The results are shown in Table 1.
<Manufacture of prints>
The thermal transfer sheet is superimposed on the surface of the dye-receiving layer of the obtained thermal transfer image-receiving sheet (IC card with a dye-receiving layer), and the output is 0.23 W / dot using a thermal head from the thermal transfer sheet side, the line speed is 1 A gradation pattern was formed on the dye-receiving layer by heating under the conditions of 0.0 ms / line and a dot density of 300 dpi, and a printed matter was produced.

(1) Releasability In the production of the printed matter, it was evaluated whether the thermal transfer sheet and the thermal transfer image receiving sheet (IC card with a dye receiving layer) can be peeled when the printed matter is produced.
(Evaluation criteria)
AA: Peelable by hand A: Somehow peelable by hand B: Unpeelable In addition, the sample whose surface of the image receiving layer was unpeelable was judged to have no evaluation value and was not performed.

(2) Print Density For the printed matter prepared as described above, the optical reflection density measured by an optical densitometer (spectrolino manufactured by Gretag Macbeth) (Ansi-A, D65), and the portion where the maximum energy is applied ( ODmax) was measured, and the print density was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The OD value was 1.8 or more.
B: The OD value was less than 1.8.

(3) Light resistance About the printed material produced as mentioned above, light resistance was evaluated with the xenon fade meter of the following conditions.
(I) Conditions for light resistance evaluation / irradiation tester: Ci4000 manufactured by Atlas
・ Light source: Xenon lamp ・ Filter: Inner side = CIRA, Outer side = Soda lime ・ Black panel temperature: 45 (℃)
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, using an optical densitometer (Macbeth RD-918, manufactured by Macbeth Co.), the optical reflection density of the Cy component of the gray image was measured with a red filter, and the optical reflection density before irradiation was 1. For the steps near 0, the change in optical density before and after irradiation was measured, the residual ratio was calculated by the following formula, and the light resistance of each thermal transfer image-receiving sheet was evaluated.
Residual rate (%) = (optical reflection density after irradiation / optical reflection density before irradiation) × 100
(Evaluation criteria)
AA: Residual rate 80% or more
A: Residual rate 70% or more and less than 80% B: Residual rate less than 70%

(4) Bleeding evaluation The IC card having the printed material was put in a 90 ° C. dry oven and stored for 5 days, and the bleeding of the image after storage was visually evaluated.
(Evaluation criteria)
A: The image looks clear without blurring B: The image blurs and blurs

(Summary of results)
In the thermal transfer recording material in which the thermal transfer sheet and the thermal transfer image-receiving sheet obtained in Examples 1 to 4 are combined, the thermal transfer sheet in which the dye layer contains a phenoxy resin as the binder resin, and the dye receiving layer is reacted with a hydroxyl group. By selecting and combining a thermal transfer image-receiving sheet, which is a cured product of a resin composition containing an agent and a hydroxyl group-containing thermoplastic resin, the image density is high and bleeding is suppressed while being excellent in releasability. A print with high quality and excellent light resistance was obtained.
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 binder resin of the dye-receiving layer used a thermal transfer image-receiving sheet containing a styrene-maleic acid resin. However, 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 used was a thermal transfer image-receiving sheet containing a vinyl chloride-vinyl acetate copolymer resin and silicone oil. The nature was also bad.
In the combination of the thermal transfer sheet and thermal transfer image-receiving sheet obtained in Comparative Example 3, the thermal transfer sheet containing the acetal resin was used as the binder resin for the dye layer, so that the releasability deteriorated and thermal fusion occurred.
In the combination of the thermal transfer sheet and the thermal transfer image-receiving sheet obtained in Comparative Example 4, the dye-receiving layer used a binder resin containing a hydroxyl group-containing thermoplastic resin but not containing a curing agent that reacts with a hydroxyl group. Deteriorated and heat fusion occurred.

DESCRIPTION OF SYMBOLS 1 Thermal transfer recording material 2 1st base material 3 Dye layer 4 Back layer 5 Dye primer layer 8 Transferable protective layer 10 Thermal transfer sheet 11 Second base material 12 Dye receiving layer 13 Intermediate layer 14 Back surface layer 20 Thermal transfer image receiving sheet 25 One base sheet member 25 ′ Second base sheet member 26, 26 ′ Adhesive 27 Inlet 28 Antenna body 29 IC chip 30 IC card 31 Reinforcing plate

Claims (6)

A thermal transfer recording material combining a thermal transfer sheet and a thermal transfer image receiving sheet,
The thermal transfer sheet is disposed on a first substrate, a dye layer containing a dye and a binder resin disposed on one surface of the first substrate, and the other surface of the first substrate. And containing a phenoxy resin as a binder resin of the dye layer,
The thermal transfer image-receiving sheet has a second substrate and a dye-receiving layer disposed on one surface of the second substrate, and the dye-receiving layer includes a hydroxyl group-containing thermoplastic resin, a hydroxyl group, A thermal transfer recording material, which is a cured product of a resin composition containing a reacting curing agent.   2. The thermal transfer recording material according to claim 1, wherein the hydroxyl group-containing thermoplastic resin is at least one of a polyvinyl butyral resin and a cellulose acetate resin.   The thermal transfer recording material according to claim 1 or 2, wherein the thermal transfer image-receiving sheet is a card having a deflection amount of 35 mm or less in a bending strength test defined in JIS X 6305-1: 2010. . A first substrate, a dye layer containing a dye and a binder resin disposed on one surface of the first substrate, and a back layer disposed on the other surface of the first substrate. Having a step of preparing a thermal transfer sheet containing a phenoxy resin as a binder resin of the dye layer;
A second substrate and a dye-receiving layer disposed on one surface of the second substrate, wherein the dye-receiving layer comprises a hydroxyl group-containing thermoplastic resin and a curing agent that reacts with a hydroxyl group. A step of preparing a thermal transfer image receiving sheet, which is a cured product of a resin composition comprising:
Superposing the dye layer surface of the thermal transfer sheet and the dye receiving layer surface of the thermal transfer image receiving sheet, thermally transferring the dye onto the dye receiving layer, and forming an image on the thermal transfer image receiving sheet, A method for producing a printed product.   The method for producing a printed matter according to claim 4, wherein the hydroxyl group-containing thermoplastic resin is at least one of a polyvinyl butyral resin and a cellulose acetate resin.   The method for producing a printed matter according to claim 4 or 5, wherein the thermal transfer image-receiving sheet is a card having a deflection amount of 35 mm or less in a bending strength test defined in JIS X 6305-1: 2010.