JP2007090782A - Protective layer transfer sheet, and printed object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer sheet for protecting an image by which a protective layer tinted with no yellow color by a heat energy or the like when the protective layer is formed can be obtained. <P>SOLUTION: This protective layer transfer sheet comprises a base material, and an ultraviolet ray absorbent copolymer for which an ultraviolet ray absorbent monomer represented by general formula (1) and an acryl based monomer are copolymerized. Then, in the ultraviolet ray absorbent copolymer, 40 mol% or higher of the ultraviolet absorbent monomer is contained for the protective layer transfer sheet. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a protective layer transfer sheet and a printed material, and particularly relates to a protective layer transfer sheet capable of providing a protective layer excellent in light resistance and the like.

  As one of various printing methods for forming an image, there is a thermal sublimation transfer in which a dye in a color material layer is sublimated and diffused by heat and transferred to an image receiving sheet. In such heat-sensitive sublimation transfer, a thermal head of a printer is usually used as a heating means, and color dots in which a large number of heating amounts of three colors or four colors are adjusted by heating for a very short time are received by the thermal transfer image receiving sheet. It is transferred to a layer and the full color of the original is reproduced with multicolored dots. The image formed in this way is very clear and excellent in transparency because the coloring material used is a dye, so the resulting image is excellent in reproducibility and gradation of intermediate colors, It is possible to form a high-quality image similar to a conventional image by offset printing or gravure printing and comparable to a full-color photographic image.

  However, the thermal sublimation transfer method described above is excellent in forming a gradation image because the amount of dye transfer can be controlled in dot units depending on the amount of energy applied, but the formed image is based on ordinary printing ink. Unlike the above, the coloring material is not a pigment but a dye having a relatively low molecular weight, and since there is no vehicle, there is a disadvantage that it is inferior in durability such as light resistance, weather resistance and abrasion resistance.

  As a means for improving the above drawbacks, a method using a reactive dye that forms an image by reacting a compound in a colorant layer with a compound in a receiving layer by thermal transfer has been proposed. For example, in Patent Documents 1 to 4, a heat diffusible dye is used as a compound to be contained on the color material layer side, a metal ion-containing compound is used as a compound to be contained in a receiving layer, and these are reacted after heat transfer to cause heat diffusibility A method of forming an image by forming a dye-metal ion-containing compound complex (hereinafter sometimes referred to as a post-chelation method) is disclosed.

  The image formed by the post-chelation method is less susceptible to dye fading and bleeding even when left at a high temperature and high humidity for a long time, and is excellent in light resistance as compared with an image obtained by a conventional method. . However, even an image formed by the post-chelation method may have insufficient durability such as light resistance, weather resistance, and wear resistance.

  As means for improving the durability, a method of providing a protective layer on a receiving layer on which an image is formed has recently been proposed. When a protective layer is provided on the receiving layer, physical resistance such as durability such as light resistance, weather resistance, and abrasion resistance as described above can be improved. In addition, by adding an ultraviolet absorber in the protective layer, the dye can be prevented from being altered or decomposed, and light resistance can be improved.

  When a protective layer is provided on an image formed by the post-chelation method described above, the image is superior in light resistance to an image formed by a normal method, and therefore the protective layer does not need to contain an ultraviolet absorber. However, it is possible to achieve sufficient light resistance to some extent, but it is preferable to contain an ultraviolet absorber in order to further improve the light resistance. At this time, depending on the intensity of thermal energy when the protective layer is thermally transferred, the UV absorber in the protective layer and the heat diffusible dye-metal ion-containing compound complex in the receiving layer may react. When the ultraviolet absorber is coordinated to the metal ion, the absorption region of the ultraviolet absorber is shifted to the visible light region, and as a result, there is a problem that it becomes yellowish.

JP 59-78893 A JP 59-109394 A Japanese Unexamined Patent Publication No. 60-2398 JP 2000-263828 A

  The present invention has been made in view of the above problems, and is a protective layer transfer sheet used for forming a protective layer for protecting an image obtained by a post-chelation method, and forms a protective layer. The main object of the present invention is to provide a protective layer transfer sheet capable of obtaining a protective layer that does not have a yellowish color due to the heat energy at the time.

  In the present invention, after transferring the thermal diffusible dye to a thermal transfer image-receiving sheet having a receiving layer containing a metal ion-containing compound capable of reacting with a chelatable thermal diffusible dye, the surface of the receiving layer is A protective layer transfer sheet used for forming a protective layer to be protected, comprising: a base material; and a protective layer forming layer formed on the base material. Formula (1)

A UV-absorbing copolymer obtained by copolymerizing an ultraviolet-absorbing monomer and an acrylic monomer, and the UV-absorbing monomer contains 40 mol% or more in the UV-absorbing copolymer. A protective layer transfer sheet is provided.

  According to the present invention, the protective layer is formed using the protective layer transfer sheet of the present invention by using the ultraviolet absorbing copolymer containing a large amount of the ultraviolet absorbing monomer represented by the general formula (1). In this case, a protective layer that does not have a yellowish color can be obtained. In addition, when trying to further improve the light resistance, in addition to the above-mentioned UV-absorbing copolymer, an ultraviolet absorber that is not a copolymer type having low reactivity with the metal ion-containing compound may be selected and added in an appropriate amount. . Preferred ultraviolet absorbers include benzotriazoles.

  Moreover, in the said invention, it is preferable that the absorption maximum wavelength of the said ultraviolet absorptive copolymer exists in the range of 310-360 nm. This is because the effect is small when it is less than 310 nm, and when it exceeds 360 nm, the yellowness of the printed matter becomes strong, and the appearance of the printed matter becomes defective.

  Moreover, in the said invention, it is preferable that the said layer for protective layer formation contains the hindered amine light stabilizer with a molecular weight of 1500 or more. The above light stabilizer can capture radicals generated by light irradiation and the like, and can further improve the light resistance of the protective layer. Further, by using a high molecular weight type hindered amine light stabilizer, This is because there is no bleeding of the stabilizing material on the surface of the protective layer, and the storage stability is excellent.

  In the present invention, there is also provided a printed matter using the above protective layer transfer sheet. In the present invention, by using the protective layer transfer sheet, it is possible to obtain a printed material having a protective layer having the above-described properties, and excellent durability such as light resistance, weather resistance, and abrasion resistance. A print can be obtained.

  In this invention, there exists an effect that the protective layer transfer sheet which can provide the protective layer excellent in light resistance etc. can be obtained.

  Hereinafter, the protective layer transfer sheet and the printed material of the present invention will be described.

A. Protective layer transfer sheet The protective layer transfer sheet of the present invention is obtained by transferring the thermal diffusible dye to a thermal transfer image-receiving sheet provided with a receiving layer containing a metal ion-containing compound capable of reacting with a chelatable thermal diffusible dye. And a protective layer transfer sheet used to form a protective layer for protecting the surface of the receiving layer, comprising: a base material; and a protective layer forming layer formed on the base material. The layer forming layer has the following general formula (1)

A UV-absorbing copolymer obtained by copolymerizing an ultraviolet-absorbing monomer and an acrylic monomer, and the UV-absorbing monomer contains 40 mol% or more in the UV-absorbing copolymer. It is characterized by that. In the present invention, it is particularly preferable that the ultraviolet absorbing monomer is contained in the ultraviolet absorbing copolymer within a range of 40 to 90 mol%, particularly 50 to 70 mol%.

  In the present invention, the content of the ultraviolet absorbing monomer is determined by 1H-NMR (nuclear magnetic resonance measurement) analysis and GPC (gel permeation chromatography) analysis at the average weight molecular weight and maximum absorption wavelength of the copolymer. It can be determined from the absorbance.

  Moreover, in this invention, it is preferable that the absorption maximum wavelength of the said ultraviolet absorptive copolymer exists in the range of 310-360 nm, especially the range of 330-350 nm. This is because the effect is small when it is less than 310 nm, and when it exceeds 360 nm, the yellowness of the printed matter becomes strong, and the appearance of the printed matter becomes defective. In addition, when trying to further improve the light resistance, in addition to the above-mentioned UV-absorbing copolymer, it is possible to select and add an appropriate amount of an UV absorber that is not a copolymer type having low reactivity with the metal ion-containing compound. good. As the ultraviolet absorber, for example, a benzotriazole type is preferable, and the addition amount is preferably 50% by weight or less based on the copolymer type ultraviolet absorber (the ultraviolet absorbing monomer).

According to the present invention, the protective layer is formed using the protective layer transfer sheet of the present invention by using the ultraviolet absorbing copolymer containing a large amount of the ultraviolet absorbing monomer represented by the general formula (1). In this case, a protective layer that does not have a yellowish color can be obtained. In the present invention, “not yellowish” means that the color difference (ΔE * ab) obtained by a test described later satisfies ΔE * ab <3. Specifically, after transferring the protective layer to the image receiving paper containing the metal ion-containing compound, the image receiving paper (printed product) is placed in an oven at 110 ° C. for 3 minutes, and the hue change (color difference) of the image receiving paper before and after the image is shown below. It was calculated from the equation and correlated with visual observation.
Color difference ΔE * ab = ((Δa *) ² + (Δb *) ² ) ^1/2
CIE1976 La * b * color system (JIS Z8729 (1980)) reference Δa * = a * (after oven storage)-a * (before oven storage)
Δb * = b * (after oven storage) -b * (before oven storage)

  In addition, the reason why the commonly used protective layer containing an ultraviolet absorber is yellowish is that the ultraviolet absorber in the protective layer and the heat-diffusible dye-metal ion-containing compound complex in the receiving phase are It is considered that this is because the absorption region of the ultraviolet absorber shifts to the visible light region by causing the reaction and the coordination of the ultraviolet absorber to the metal ion. In the present invention, since the ultraviolet absorbing monomer represented by the general formula (1) has N and OH, similarly to a general ultraviolet absorber, a heat diffusible dye-metal ion-containing compound complex. It is believed that a yellowish protective layer is formed, and in the present invention, a UV-absorbing copolymer containing a large amount of the UV-absorbing monomer represented by the general formula (1) is used. Since it uses, it is thought that the protective layer with more yellowishness is formed. However, in the present invention, the reason is not yet clear, but by using the ultraviolet absorbing copolymer, a protective layer that does not have a yellowish color can be obtained, and the ultraviolet absorbing copolymer is Since it contains a large amount of an ultraviolet-absorbing monomer, a protective layer having excellent light resistance can be obtained. One of the reasons why the UV-absorbing copolymer is excellent in light resistance is that, in the case of a monomer UV absorber, diffusion of the UV absorber occurs in the receiving layer during transfer of the protective layer, so that It is conceivable that the ability to cut the ultraviolet rays will decrease.

Next, the protective layer transfer sheet of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the protective layer transfer sheet of the present invention. The protective layer transfer sheet of the present invention comprises a substrate 1 and a protective layer forming layer 2 formed on one surface of the substrate 1. In addition, as shown in FIG. 2, the protective layer transfer sheet of the present invention includes a release layer 3 between the substrate 1 and the protective layer forming layer 2, and is opposite to the protective layer forming layer 2. The back surface layer 4 may be provided on the surface of the substrate 1 on the side.
Hereinafter, the protective layer transfer sheet of the present invention will be described in detail.

1. Protective layer forming layer The protective layer forming layer used in the present invention will be described. The protective layer forming layer used in the present invention becomes a protective layer by being transferred onto the receiving layer on which the image is printed. The protective layer-forming layer contains at least an ultraviolet absorbing copolymer described later.

(1) Ultraviolet-absorbing copolymer The ultraviolet-absorbing copolymer used in the present invention is represented by the following general formula (1).

Is obtained by copolymerizing an ultraviolet-absorbing monomer represented by formula (II) and an acrylic monomer.

  The ultraviolet absorbing copolymer used in the present invention is not particularly limited as long as it is obtained by copolymerizing the ultraviolet absorbing monomer and the acrylic monomer. Specifically, Examples thereof include random copolymers and graft copolymers of the above materials.

  The weight-average molecular weight of the UV-absorbing copolymer used in the present invention is not particularly limited as long as a desired protective layer-forming layer can be obtained. Specifically, the weight-average molecular weight is 5000 to 250,000. Within the range, in particular, within the range of 9000 to 40000 is preferable.

  In addition, the glass transition temperature (Tg) of the ultraviolet absorbing copolymer used in the present invention is not particularly limited as long as a desired protective layer forming layer can be obtained. It is preferably in the range of 105 ° C., particularly in the range of 45 to 95 ° C.

  Next, the acrylic monomer used in the present invention will be described. The molecular weight of the acrylic monomer used in the present invention is not particularly limited as long as a desired UV-absorbing copolymer can be obtained. Specifically, the molecular weight is within the range of 5000 to 250,000. Especially, it is preferable to be in the range of 9000 to 40000.

Specific examples of such acrylic monomers include cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and dicyclopentenyl. Acrylate, dicyclopentenyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary Butyl methacrylate, isodecyl acrylate Isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, lauryl tridecyl acrylate, lauryl tridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, cetyl stearyl acrylate, cetyl stearyl methacrylate, stearyl acrylate, stearyl methacrylate, 2- Ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclope Tenenyl acrylate, dicyclopentenyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate Acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, tertiary butylaminoethyl acrylate, tertiary butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, ethylene diacrylate, ethylene di Methacrylate, diethylene glycol Diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol diacrylate, decaethylene glycol dimethacrylate, pentadecaethylene Glycol diacrylate, pentadecaethylene glycol dimethacrylate, pentacontahector ethylene glycol diacrylate, pentacontahector ethylene glycol dimethacrylate, butylene diacrylate, butylene dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimeta Chryrate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate, tripyropyrene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexa Examples thereof include acrylate, dipentaerythritol hexamethacrylate, neopentyl glycol pentaacrylate, neopentyl glycol pentamethacrylate, phosphazene hexaacrylate, and phosphazene hexamethacrylate.
In the present invention, among the acrylic monomers, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, phenoxyethyl acrylate, methyl methacrylate, acrylic acid, and acrylonitrile are preferable.

(2) Other components In addition to the ultraviolet absorbing copolymer, the protective layer forming layer used in the present invention is an ultraviolet absorber other than the ultraviolet absorbing monomer represented by the general formula (1), light It may contain a stabilizer, an antioxidant, a fluorescent brightening agent, a filler and the like.
The ultraviolet absorber is not particularly limited as long as a protective layer not yellowish can be obtained, and specifically, salicylate-based, benzophenone-based, benzotriazole-based, triazine-based, substituted acrylonitrile-based , Nickel chelate-based, hindered amine-based ultraviolet absorbers, etc., among which benzotriazole-based ultraviolet absorbers are preferred. Such a benzotriazole-based ultraviolet absorber is not particularly limited, but specifically, the following general formula (2) and general formula (3)

The thing etc. which are represented by can be mentioned. The usage-amount of the said ultraviolet absorber will not be specifically limited if the protective layer which does not get yellowish can be obtained, It can select arbitrarily.

  The light stabilizer used in the present invention is used for capturing radicals generated by light irradiation or the like and further improving the light resistance of the protective layer. Although the molecular weight of the said light stabilizer is not specifically limited, Specifically, it is preferable that it is 1500 or more, and it is preferable to exist in the range of 1500-4000 especially. In addition, the light stabilizer is not particularly limited, and specific examples include hindered amine-based, phenol-based, and phosphite-based light stabilizers. System light stabilizers are preferred. The usage-amount of the said light stabilizer is not specifically limited unless the function of the said ultraviolet absorptive copolymer etc. is inhibited, It can select arbitrarily.

(3) Protective layer forming layer The thickness of the protective layer forming layer used in the present invention is not particularly limited as long as desired durability and the like can be obtained, but specifically 0.1 to 10 μm. It is preferable that it exists in the range of 0.5-5 micrometers among these.

  The protective layer forming layer used in the present invention may have a single layer structure or a multilayer structure. When the protective layer forming layer has a multilayer structure, the layer structure is not particularly limited as long as it is two or more layers, and an arbitrary layer structure can be adopted. The protective layer forming layer may have an adhesive layer on the surface. In this case, the protective layer forming layer and the adhesive layer can be regarded as the protective layer forming layer in the present invention. Therefore, when the protective layer-forming layer has an adhesive layer on the surface, the ultraviolet absorbing copolymer may be contained in at least one of the protective layer-forming layer and the adhesive layer. In addition, it does not specifically limit as resin for protective layer formation, The material similar to the material used for a general protective layer transfer sheet can be used. Specific examples include polyester resins, acrylic resins, acetal resins, polystyrene resins, polyurethane resins, acrylic urethane resins, polycarbonate resins, vinyl chloride vinyl acetate copolymer resins, polyamide resins, norbornene resins, and the like. A resin obtained by modifying the resin with silicone, a mixture of these resins, and the like can be added as necessary.

  Further, the method for producing the protective layer forming layer used in the present invention is not particularly limited. For example, a coating liquid containing a material constituting the protective layer forming layer is prepared and described later. The method of apply | coating to a base material is mentioned. Examples of the coating method at this time include a gravure coating method, a gravure reverse coating method, and a roll coating method.

2. Substrate Next, the substrate used in the present invention will be described. In the present invention, the protective layer forming layer is formed on the substrate. Specific examples of such a substrate include thin papers such as glassine paper, condenser paper, and paraffin paper, polyethylene terephthalate, polyethylene telenaphthalate, polyphenylene sulfide, polyether ketone, polyether sulfone, and other highly heat-resistant polyester, polypropylene. , Polycarbonate, cellulose acetate, polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, ionomer, and other plastic stretched or unstretched films, and laminates of these materials. Among these, polyethylene terephthalate and polyethylene terephthalate are preferable.

  The thickness of the base material can be appropriately selected depending on the material so that the strength, thermal conductivity, heat resistance and the like are appropriate, but usually about 1 to 100 μm is preferably used. The base material is preferably subjected to primer treatment or corona treatment on the surface.

3. Back layer and release layer The protective layer transfer sheet of the present invention may comprise at least one of a back layer and a release layer. For example, as shown in FIG. 2, the back layer 3 is provided on the surface of the base material 1 opposite to the protective layer forming layer 2, and heat fusion between a heating device such as a thermal head and the base material is performed. It is provided for the purpose of preventing and smooth running. Similarly, as shown in FIG. 2, the release layer 4 is provided between the base material 1 and the protective layer forming layer 2, and improves the releasability of the protective layer forming layer 2 during thermal transfer. It is provided for this purpose. Such a back layer and a release layer are not particularly limited, and examples thereof include those described in JP-A No. 2001-347759.

4). Thermal Transfer Image Receiving Sheet Next, the thermal transfer image receiving sheet to which the protective forming layer of the protective layer transfer sheet is transferred will be described. The thermal transfer image-receiving sheet usually has a support and a receiving layer formed on the support, and the receiving layer is a metal ion-containing compound that can react with a chelatable heat-diffusible dye. It contains.

  In the thermal transfer image-receiving sheet, when the thermal diffusible dye is transferred to the receptor layer, the thermal diffusible dye reacts with the metal ion-containing compound, and the thermal diffusible dye-metal ion-containing compound complex. Thus, an image is formed. The image formed in this manner is less susceptible to dye fading and bleeding even when left at high temperature and high humidity for a long time, and exhibits excellent light resistance as compared with conventional thermal sublimation transfer. In order to form an image formed by the above method and a protective layer for protecting the surface of the receiving layer, the protective layer transfer sheet of the present invention is used.

(1) Receiving layer The receiving layer used for the thermal transfer image-receiving sheet usually contains the metal ion-containing compound and a binder resin.

(A) Metal ion-containing compound The metal ion-containing compound used in the receptor layer of the thermal transfer image-receiving sheet reacts with a heat-diffusible dye described later to form a heat-diffusible dye-metal ion-containing compound complex in the receptor layer. To do.
Although it does not specifically limit as content in the receiving layer of the said metal ion containing compound, 5 to 80 weight% is preferable with respect to the binder resin mentioned later, and 10 to 70 weight% is more preferable.

The metal ion-containing compound used in the receiving layer of the thermal transfer image-receiving sheet is not particularly limited, and examples thereof include inorganic or organic salts of metal ions and metal complexes, among which salts of organic acids and Complexes are preferred. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table, among which Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti, and Zn is preferable, Ni, Cu, Cr, Co and Zn are more preferable, and Ni is particularly preferable. Specific examples of such metal ion-containing compounds include Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and aliphatic salts such as acetic acid and stearic acid, or aromatics such as benzoic acid and salicylic acid. Examples thereof include carboxylic acid salts. Moreover, the complex represented by the following general formula (5) can be particularly preferably used.

General formula (5) [M (Q ₁ ) 1 (Q ₂ ) m (Q ₃ ) n] ^{p +} (Y ⁻ ) p

However, in said formula, M represents a metal ion, Preferably Ni ^<2+> , Cu ^<2+> , Cr ^<2+> , Co ^<2+> , Zn ^<2+> . Q ₁ , Q ₂ , and Q ₃ each represent a coordination compound capable of coordination with a metal ion represented by M, and may be the same or different from each other. These coordination compounds can be selected from, for example, coordination compounds described in Chelate Science 5 (Keihei Ueno, Nanedo, 1975). Y represents an organic anion group, and specific examples include a tetraphenyl boron anion and an alkylbenzene sulfonate anion. l represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. In these, the complex represented by the above general formula is tetradentate or hexadentate. It is determined depending on whether it is coordinated or determined based on the number of ligands of Q ₁ , Q ₂ , and Q ₃ . P represents 0, 1 or 2. P = 0 indicates that the coordination compound represented by Q is an anionic compound, and the anionic compound represented by Q and the metal cation represented by M are electrically neutralized. means.

  As the anionic compound, a compound represented by the following general formula (6) is preferable.

In the formula, R ₁ and R ₃ may be the same or different and each represents an alkyl group or an aryl group, and R ₂ represents an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a hydrogen atom. R ₁ , R ₂ and R ₃ may be substituted with the same substituent as the substituent represented by R ₁₁ in the general formula (I) described later.

  In the present invention, the metal ion-containing compound is particularly preferably a compound represented by the following structural formula.

(B) Binder resin The binder resin used in the receiving layer of the thermal transfer image-receiving sheet is not particularly limited as long as the dye is easily dyed, and known ones can be used. Specifically, polyolefin resins such as polypropylene; halogenated resins such as polyvinyl chloride and polyvinylidene chloride; copolymers of halogenated resins such as vinyl chloride vinyl acetate copolymer resins and other vinyl monomers; polyacetic acid Vinyl resins such as vinyl, polyacrylic acid ester, polyvinyl acetal, polyvinyl butyral; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polystyrene resins, polyamide resins, phenoxy resins, olefins such as ethylene and propylene, and other vinyls Polyurethanes; Polycarbonates; Acrylic resins; Ionomers; Cellulose derivatives, etc. Among these, copolymer resins of halogenated resins and other vinyl monomers, poly Ester-based resins and vinyl resins are preferred. The binder resin may be used alone or in a mixture.

(2) Support The support used for the thermal transfer image-receiving sheet has a role of holding the receiving layer, and heat is applied at the time of thermal transfer, so that there is no problem in handling even in an overheated state. It is preferable to have strength.

  The material of such a support is not particularly limited. For example, condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin-based, polystyrene-based), fine paper, art paper, coated 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, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyether Imide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, Examples include films of polyethersulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene-ethylene, tetrafluoroethylene-hexafluoropropylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and the like. A white opaque film formed by adding a white pigment or filler to these synthetic resins or a foamed foam sheet can also be used. Furthermore, the laminated body by arbitrary combinations of the said support body can also be used.

  For the purpose of increasing the adhesive strength between the support and the receiving layer, it is preferable to subject the surface of the support to various primer treatments and corona discharge treatments.

(3) Thermally diffusible dye Next, the thermally diffusible dye which reacts with the said metal ion containing compound is demonstrated. The thermal diffusible dye is usually contained in an ink layer of an ink sheet, and the thermal diffusible dye is heated by a thermal head or the like by overlapping the ink layer and the receiving layer so as to face each other. Transfer to the receiving layer of the thermal transfer image receiving sheet.
The ink layer of the ink sheet according to the present invention should not cause problems such that the dye is likely to be thermally diffused and the dye is bleed during storage or thermally fused to the image receiving sheet during thermal transfer. However, it is not particularly limited, and known ones can be used. Specifically, acrylic resins and derivatives thereof, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyimide, polyvinyl acetal, polyvinyl butyral, polyester resin, polyurethane resin, vinyl chloride vinyl acetate copolymer resin, nitrocellulose, ethyl cellulose, acetic acid Examples thereof include cellulose such as cellulose and derivatives thereof.

  The heat diffusible dye in the present invention is not particularly limited as long as it can chelate with the metal ion-containing compound described above, and general cyan dyes, magenta dyes, yellow dyes and the like are used. be able to. Especially, in this invention, it is preferable that it is a heat | fever diffusible dye represented by the following general formula (I)-(V).

  (A) Thermally diffusible dye represented by the general formula (I)

(Wherein R ₁₁ represents a substituent, R ₁₂ represents an alkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group, R ₁₃ and R ₁₄ represent a hydrogen atom or a substituent, and R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a hydrogen atom, an alkyl group, or an aryl group, and Z ₁₁ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

The substituent represented by R ₁₁ is not particularly limited. For example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.) ), Alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkenyl group (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl) Group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, Chlorohexenyl group, etc.), halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group) Etc.), alkylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl groups (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl groups (eg, methylsulfinyl group, etc.), arylsulfinyl groups (For example, phenylsulfinyl group), phosphono group, acyl group (acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, Cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylamino) Sulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), cyano Group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group, Roxy group, acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (eg, amino group, ethylamino group, dimethylamino group, butylamino) Group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, Ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), alkoxycarbonylamido Group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), complex Examples thereof include a ring thio group, a thioureido group, a carboxyl group, a salt of a carboxylic acid, a hydroxyl group, a mercapto group, and a nitro group.

  These substituents may be further substituted with the same substituent.

As R ₁₁ , an alkyl group, a cycloalkyl group, an aryl group, a cyano group, an alkoxy group, an amino group, and an alkoxycarbonyl group are preferable, and an alkyl group is particularly preferable. In the general formula (I), R ₁₂ represents an alkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group. Examples of the alkyl group, alkenyl group, alkynyl group or cycloalkyl group represented by R ₁₂ include the same groups as the alkyl group, alkenyl group, alkynyl group or cycloalkyl group in the above R ₁₁ .

The alkyl group, alkenyl group, alkynyl group or cycloalkyl group represented by R ₁₂ may be substituted with the same substituent as the substituent represented by R ₁₁ .
R ₁₂ is preferably an alkyl group.

In the general formula (I), R ₁₃ and R ₁₄ represent a hydrogen atom or a substituent. Examples of the substituent represented by R ₁₃ and R ₁₄ include the same groups as the substituent represented by R ₁₁ , and these substituents may be further substituted with the same substituent. As R ₁₃ and R ₁₄ , a hydrogen atom, an alkyl group, and an aryl group are preferable, and a hydrogen atom is particularly preferable.

In the general formula (I), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a hydrogen atom, an alkyl group or an aryl group. Examples of the alkyl group and aryl group represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ include the same groups as the alkyl group and aryl group in R ₁₁ .

The alkyl group and aryl group represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ may be substituted with the same substituent as the substituent represented by R ₁₁ .
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are preferably a hydrogen atom.

In the general formula (I), Z ₁₁ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

Specific examples of such a heterocyclic ring include pyridine ring, pyrazole ring, imidazole ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, oxazole ring, quinoline ring, benzothiazole ring, benzoxazole ring and the like. be able to. A pyridine ring, a pyrazole ring and an imidazole ring are preferable, and a pyridine ring is particularly preferable. These rings may have a substituent, and examples of the substituent include the same groups as the substituent represented by R ₁₁ above.

  In the present invention, among the heat diffusible dyes represented by the general formula (I), the heat diffusible dye represented by the general formula (I-i) is preferable.

  In the present invention, a compound represented by the following structural formula (I-1) is preferably used.

  (B) Thermally diffusible dye represented by the general formula (II)

(Wherein R ₂₁ represents a trifluoromethyl group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group, a cyano group, and R ₂₂ represents represents an alkyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl _{group, R 23} represents an alkyl group, an alkenyl group, an aryl group. _However, the total number of carbon atoms contained in _{R 21} and _{R 22} is 3 or more _{.X 21} Represents —CR ₂₄ R ₂₅ —, —S—, —O—, —NR ₂₆ —, R ₂₄ and R ₂₅ represent a hydrogen atom, a halogen atom and a substituent, and R ₂₆ represents a hydrogen atom, a substituent Y ₂₁ represents a group of atoms necessary to form a 5- or 6-membered ring.

In the general formula (II), R ₂₁ represents a trifluoromethyl group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group, or a cyano group.
R ₂₁ is preferably an alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or a cyano group, and more preferably an alkyl group. Among the alkyl groups, a branched alkyl group is more preferable, and examples of the branched alkyl group include isopropyl group, tert-butyl group, isobutyl group, sec-butyl group, neo-pentyl group, tert-amyl group, and the like. Most preferred are isopropyl group and tert-butyl group.
In the present invention, the light resistance of the dye is improved by increasing R ₁₁ .

R ₂₂ represents an alkyl group, an acyl group, a carbamoyl group, or an alkoxycarbonyl group.
R ₂₂ is preferably an alkyl group, an acyl group, or a carbamoyl group, and more preferably an alkyl group. Among the alkyl groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group are particularly preferable, and a methyl group is most preferable.

R ₂₃ represents an alkyl group, an alkenyl group, or an aryl group. Preferred is an alkyl group, and among the alkyl groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group are most preferred. Methyl group, ethyl group, propyl group, isopropyl group and butyl group.

X ₂₁ represents —CR ₂₄ R ₂₅ —, —S—, —O—, —NR ₂₆ —, and preferably —CR ₂₄ R ₂₅ —, —S—, —O—.

R ₂₄ and R ₂₅ represent a hydrogen atom, a halogen atom, or a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable. Since the substituent is the same as the substituent in the general formula (I) described above, description thereof is omitted here.

  As the substituent, a hydrogen atom, an alkyl group, and an aryl group are preferable. More preferably, a hydrogen atom and an alkyl group are preferable, and among the alkyl groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group are preferable. Is most preferably a methyl group.

R ₂₆ represents a hydrogen atom or a substituent.
Examples of the substituent include the same substituents as those exemplified as R ₂₄ and R ₂₅ .

  Of these, a hydrogen atom, an alkyl group, and an aryl group are preferable. More preferably, a hydrogen atom and an alkyl group are preferable, and among the alkyl groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group are preferable. Is most preferably a methyl group.

Y ₂₁ represents an atomic group necessary for forming a 5- to 6-membered ring. Preferably, it is an atomic group necessary for forming a 6-membered ring. Examples include a cyclopentane ring, a cyclohexane ring, a benzene ring, a pyridine ring, a naphthalene ring, and the like, and a benzene ring is preferable.

  In the present invention, among the heat diffusible dyes represented by the general formula (II), the heat diffusible dyes represented by the general formulas (II-i) to (II-iv) are preferable.

  In the present invention, a compound represented by the following structural formula (II-1) is preferably used.

  (C) Thermally diffusible dye represented by the general formula (III)

(In the formula, Y ₃₁ represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₃₁ and Z ₃₂ represent —CR ₃₂ = or —N =, and L ₃₁ represents the following general formula (III-a) X ₃₁ represents an unsubstituted or substituted alkylamino group, R ₃₁ represents a substituted or unsubstituted alkyl group, n represents an integer of 0 or more, and R ₃₂ represents hydrogen. Here, σp represents an electronic parameter, and is calculated by the method described in J. Med. Chem. 16, 1207 (1973) and J. Med. Chem. 20, 304 (1977). can do.

（式中、Ｂ_３１は複素環を形成するのに必要な非金属原子群を表す。）

(In the formula, B ₃₁ represents a nonmetallic atom group necessary for forming a heterocyclic ring.)

In the general formula (III), Y ₃₁ represents a substituent of 0.2 ≦ σp ≦ 0.9, preferably 0.3 ≦ σp ≦ 0.8, more preferably 0.4 ≦ σp ≦ 0.7. Represents a substituent. When σp <0.2, the absorption wavelength becomes broad, which is not preferable. When σp> 0.9, dyeing during production is not preferable because of low yield. Specific examples of the substituent include an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group.

L ₃₁ represents a group represented by the general formula (III-a), and includes a nonmetallic atom group B ₃₁ necessary for forming a heterocyclic ring. Examples of the group represented by the general formula (III-a) include 2-pyrrolyl group, imidazolyl group, isothiazolyl group, isoxazolyl group, 3-pyrazolyl group, pyrazinyl group, triazolyl group, 2-pyridyl group, pyridazinyl group, pyrimidinyl group. It represents a 3H-indolyl group, a 1H-indazolyl group, a prynyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinosalinyl group, a quinazolinyl group, or the like. These heterocycles may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2- Methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), aryl groups (eg, phenyl, p-tolyl, naphthyl, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, etc.), alkoxy groups (eg, methoxy, ethoxy, Butoxy etc.), alkoxycarbonyl groups (eg methoxycarbonyl, i-propoxycarbonyl etc.), acyloxy groups (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio groups (eg methylthio, ethylthio, octylthio etc.), arylthio groups ( For example, phenylthio, p-tolyl O, etc.), an amino group (e.g., methylamino, diethylamino, methoxy ethylamino etc.), a cyano group, a nitro group, a Hajime Tamaki (e.g., pyridyl, pyrazolyl, imidazolyl, furyl, thienyl and the like).

X ₃₁ represents an unsubstituted or substituted alkylamino group, and examples of the substituent include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), an alkoxy group (Eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, Octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups (eg, , Methanes Sulphonamide, ethanesulfonamide, etc.), acylamino groups (eg, acetylamino, benzoylamino, etc.), carbamoyl groups (methylcarbamoyl, phenylcarbamoyl, etc.), sulfamoyl groups (eg, methylsulfamoyl, phenylsulfamoyl, etc.) It is done.

R ₃₁ represents a substituted or unsubstituted alkyl group. R ₃₂ represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), an aryl group (eg, phenyl, p-tolyl, naphthyl etc.), acyl group (eg acetyl, propionyl, benzoyl etc.), alkoxy group (eg methoxy, ethoxy, butoxy etc.), alkoxycarbonyl group (eg methoxycarbonyl, i-propoxycarbonyl etc.), Acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.) ) An ano group, a nitro group, etc. are mentioned.

  In the present invention, among the heat diffusible dyes represented by the general formula (III), the heat diffusible dyes represented by the general formulas (III-i) to (III-iii) are preferable.

  In the present invention, a compound represented by the following structural formula (III-1) is preferably used.

  (D) Thermally diffusible dye represented by the general formula (IV)

(In the formula, Y ₄₁ represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₄₁ and Z ₄₂ represent —CR ₄₃ = or —N =, and L ₄₁ represents the general formula (IV-a), Represents a group represented by (IV-b), X ₄₁ represents an unsubstituted or substituted alkylamino group, R ₄₁ represents a substituted or unsubstituted alkyl group, and R ₄₃ represents a hydrogen atom or a substituent. And n represents an integer of 0 or more.)

(Wherein R ₄₂ represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a mercapto group, an alkylthio group, or an arylthio group, Rb represents a substituent, p represents an integer of 0 to 4, and B represents − This represents a nonmetallic atom group necessary for forming a heterocyclic ring together with CR ₄₂ =.)

In the general formula (IV), Y ₄₁ represents a substituent of 0.2 ≦ σp ≦ 0.9, preferably 0.3 ≦ σp ≦ 0.8, more preferably 0.4 ≦ σp ≦ 0.7. Represents a substituent. When σp <0.2, the absorption wavelength becomes broad, which is not preferable. When σp> 0.9, dyeing during production is not preferable because of low yield.

L ₄₁ represents a group represented by general formula (IV-a) or (IV-b), and represents a group that forms a heterocyclic ring with -CR ₄₂ = and B ₄₁ represented by general formula (IV-a). Is a pyrrolyl group, imidazolyl group, isothiazolyl group, isoxazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, 3H-inddolyl group, 1H-indazolyl group, purinyl group, isoquinolyl group, quinolyl group Group, phthalazinyl group, naphthyridinyl group, quinosalinyl group, quinazolinyl group and the like. R ₄₂ represents a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), an aryloxy group, an amino group (eg, methylamino, diethylamino, methoxyethylamino, etc.), a mercapto group, an alkylthio group (eg, methylthio, ethylthio, octylthio, etc.) Represents an arylthio group (for example, phenylthio, p-tolylthio and the like). These heterocyclic rings may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom and a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, Trifluoromethyl, 2-ethylhexyl, etc.), aryl groups (eg phenyl, p-tolyl, naphthyl etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy Groups (for example, phenoxy, naphthoxy, etc.), alkoxycarbonyl groups (for example, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (for example, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (for example, methylthio, ethylthio, octylthio, etc.), arylthio Base For example phenylthio, p- tolylthio, etc.), an amino group (e.g. methylamino, diethylamino, methoxy ethylamino etc.), a cyano group, a nitro group, a Hajime Tamaki (e.g. pyridyl, pyrazolyl, imidazolyl, furyl, thienyl and the like).

X ₄₁ represents an unsubstituted or substituted alkylamino group, and examples of the substituent include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), an alkoxy group (Eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, Octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups (eg, , Methanes Sulphonamide, ethanesulfonamide, etc.), acylamino groups (eg, acetylamino, benzoylamino, etc.), carbamoyl groups (methylcarbamoyl, phenylcarbamoyl, etc.), sulfamoyl groups (eg, methylsulfamoyl, phenylsulfamoyl, etc.) It is done.

R ₄₁ represents a substituted or unsubstituted alkyl group. R ₄₃ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), an aryl group (for example, phenyl, p- Tolyl, naphthyl, etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy groups (eg phenoxy, naphthoxy etc.), alkoxycarbonyl groups (eg methoxycarbonyl, i -Propoxycarbonyl etc.), acyloxy groups (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio groups (eg methylthio, ethylthio, octylthio etc.), arylthio groups (eg phenylthio, p-tolylthio etc.), amino groups (eg Tilamino, diethylamino and the like), cyano group, nitro group and the like.

  Examples of the substituent represented by Rb include a halogen atom (for example, a fluorine atom and a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), aryl Groups (eg phenyl, p-tolyl, naphthyl etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy groups (eg phenoxy, naphthoxy etc.), alkoxycarbonyl Groups (for example, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (for example, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (for example, methylthio, ethylthio, octylthio, etc.), arylthio groups (for example, phenylthio, p-tolylthio) Etc.), amino groups (e.g. methylamino, diethylamino, methoxy ethylamino etc.), a cyano group, a nitro group, a Hajime Tamaki (e.g. pyridyl, pyrazolyl, imidazolyl, furyl, and thienyl), and the like.

  In the present invention, among the heat diffusible dyes represented by the general formula (IV), the heat diffusible dyes represented by the general formulas (IV-i) to (IV-iii) are preferable.

  In the present invention, a compound represented by the following structural formula (IV-1) is preferably used.

  (E) Thermally diffusible dye represented by the general formula (V)

(In the formula, R ₅₁ and R ₅₂ each represent a substituted or unsubstituted aliphatic group, R ₅₃ represents a substituent, n represents an integer of 0 to 4, and when n is 2 or more, R ₅₃ may be the same or different, and R ₅₅ and R ₅₆ each represents an alkyl group, provided that at least one of R ₅₅ and R ₅₆ represents a secondary alkyl group.

In the general formula (V), R ₅₁ and R ₅₂ represent a substituted or unsubstituted aliphatic group, and R ₅₁ and R ₅₂ may be the same or different. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, and the like. Examples of the group that can replace these alkyl groups include a linear or branched alkyl group (for example, a methyl group, Ethyl group, i-propyl group, t-butyl group, n-dodecyl group, 1-hexylnonyl group and the like), cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, And adamantyl group, etc.), and alkenyl groups (eg 2-propylene group, oleyl group etc.), aryl groups (eg phenyl group, ortho-tolyl group, ortho-anisyl group, 1-naphthyl group, 9-anthranyl group etc.), Heterocyclic groups (for example, 2-tetrahydrofuryl group, 2-thiophenyl group, 4-imidazolyl group, 2-pyridyl group, etc.), Gen atom (for example, fluorine atom, chlorine atom, bromine atom), cyano group, nitro group, hydroxy group, carbonyl group (for example, alkylcarbonyl group such as acetyl group, trifluoroacetyl group, pivaloyl group, benzoyl group, pentafluorobenzoyl) Group, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl group), oxycarbonyl group (for example, alkoxycarbonyl group such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group) Aryloxycarbonyl groups such as phenoxycarbonyl group, 2,4-di-t-amylphenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-pyridyloxycarbonyl group, 1-phenylpyrazolyl-5-oxycarbonyl group, etc. of Oxycyclic carbonyl group), carbamoyl group (for example, dimethylcarbamoyl group, alkylcarbamoyl group such as 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, phenylcarbamoyl group, 1-naphthylcarbamoyl group, etc. Arylcarbamoyl group), alkoxy group (for example, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl)) Phenoxy group etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group etc.) Group, benzoyloxy group, Aryl urethane groups such as n-fluorobenzoyloxy group), urethane groups (eg, alkyl urethane groups such as N, N-dimethylurethane group, aryl urethanes such as N-phenylurethane group, N- (p-cyanophenyl) urethane group) Group), a sulfonyloxy group (for example, an alkylsulfonyloxy group such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, n-dodecanesulfonyloxy group, arylsulfonyloxy group such as benzenesulfonyloxy group, p-toluenesulfonyloxy group) Amino groups (for example, alkylamino groups such as dimethylamino group, cyclohexylamino group, n-dodecylamino group, arylamino groups such as anilino group, pt-octylanilino group, etc.), sulfonylamino groups (for example, methanesulfonyl) amino , Alkylsulfonylamino groups such as heptafluoropropanesulfonylamino group and n-hexadecylsulfonylamino group, arylsulfonylamino groups such as p-toluenesulfonylamino group and pentafluorobenzenesulfonylamino), sulfamoylamino groups (for example, N , Alkylsulfamoylamino groups such as N-dimethylsulfamoylamino group, arylsulfamoylamino groups such as N-phenylsulfamoylamino group), acylamino groups (eg alkyl such as acetylamino group and myristoylamino group) Arylcarbonylamino group such as carbonylamino group, benzoylamino group), ureido group (for example, alkylureido group such as N, N-dimethylaminoureido group, N-phenylureido group, N- (p-cyanophenyl) ureido Arylsulfide groups such as methanesulfonyl group, alkylsulfonyl groups such as trifluoromethanesulfonyl group, and arylsulfonyl groups such as p-toluenesulfonyl group), sulfamoyl groups (such as dimethylsulfamoyl group, 4- (2,4-di-t-amylphenoxy) alkylsulfamoyl groups such as butylaminosulfonyl group, arylsulfamoyl groups such as phenylsulfamoyl group), alkylthio groups (for example, methylthio group, t-octylthio group, etc.) ), An arylthio group (for example, phenylthio group), and a heterocyclic thio group (for example, 1-phenyltetrazol-5-thio group, 5-methyl-1,3,4-oxadiazole-2-thio group). Can be mentioned.

  Examples of the cycloalkyl group and the alkenyl group are the same as the above substituents. Examples of the alkynyl group include 1-propyne, 2-butyne, 1-hexyne and the like.

It is also preferred that R ₅₁ and R _{52 form} a non-aromatic cyclic structure (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.).

R ₅₃ represents a substituent, and examples of the substituent include the substituents of R ₅₁ and R ₅₂ described above. Among the above substituents, an alkyl group, a cycloalkyl group, an alkoxy group, and an acylamino group are preferable. n represents an integer of 0 to 4, and when n is 2 or more, the plurality of R ₅₃ may be the same or different.

R ₅₅ and R ₅₆ represent an alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an isopropyl group, Examples thereof include a sec-butyl group, a tert-butyl group, a 3-heptyl group, and a 2-ethylhexyl group. At least one of R ₅₅ and R ₅₆ represents a secondary alkyl group, and examples of the secondary alkyl group include an isopropyl group, a sec-butyl group, a 3-heptyl group, and a 2-ethylhexyl group. The most preferred substituent as the secondary alkyl group for R ₅₅ and R ₅₆ is an isopropyl group. The secondary alkyl group of R ₅₆ may be substituted, but is all substituted with a substituent consisting of a carbon atom and a hydrogen atom, and is not substituted with a substituent containing other atoms. _R55 and _R56 may be the same or different.

  In the present invention, among the heat diffusible dyes represented by the general formula (V), the heat diffusible dyes represented by the general formulas (Vi) to (V-iii) are preferable.

  In the present invention, a compound represented by the following structural formula (V-1) is preferably used.

B. Printed matter Next, the printed matter of the present invention will be described. The printed matter of the present invention is characterized by using the above protective layer transfer sheet. That is, the printed matter of the present invention transfers a thermal diffusible dye to a thermal transfer image-receiving sheet provided with a receiving layer containing a metal ion-containing compound capable of reacting with a chelatable thermal diffusible dye. -A metal ion-containing compound complex is formed, and then a protective layer is formed using the protective layer transfer sheet.

  In the present invention, by using the protective layer transfer sheet, it is possible to obtain a printed material having a protective layer having the above-described properties, and excellent durability such as light resistance, weather resistance, and abrasion resistance. A print can be obtained.

  The protective layer, the thermal transfer image-receiving sheet, and the thermal diffusible dye in the printed product of the present invention are the same as those described in the above “A. Protective layer transfer sheet”, and thus description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Hereinafter, the present invention will be specifically described with reference to examples. In this example, “part” means part by weight unless otherwise specified.
[Examples 1 to 11 and Comparative Examples 1 to 17]
In Examples 1 to 11 and Comparative Examples 1 to 17, as shown in FIG. 3, the substrate 1, the back layer 4 formed on one surface of the substrate 1, and the other surface of the substrate 1 The protective layer forming layer 2 is formed, and the protective layer forming layer 2 has an adhesive layer 5 on the surface. In Examples 1 to 11 and Comparative Examples 1 to 17, the adhesive layer 5 contains an ultraviolet absorbing polymer.

As a base sheet, a polyethylene terephthalate film (PET) having a thickness of 4.5 μm was used, and a dry coating amount of 1.0 g / m was applied on this surface by gravure coating with a back layer coating solution prepared in advance in the following composition. ² was applied to form a back layer.
(Back layer coating solution)
Polyvinyl butyral resin (ESREC BX-1 Sekisui Chemical Co., Ltd.) 13.6 parts Polyisocyanate curing agent (Takenate D218 Takeda Pharmaceutical Co., Ltd.) 0.6 parts Phosphate ester (Plysurf A208S Daiichi Kogyo Seiyaku) 0.8 parts Methyl ethyl ketone 42.5 parts Toluene 42.5 parts

Next, on the surface of the base sheet opposite to the surface on which the back layer is formed, the protective layer-forming layer coating solution prepared to the following composition is dried by a bar coater so that the film thickness becomes 1.0 μm. To form a protective layer-forming layer. In addition, when drying the said protective layer forming layer, it dried with the dryer, and also left still for 1 minute in oven with a temperature of 100 degreeC.
(Protective layer forming layer coating solution)
Acrylic resin (BR-87 manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts Toluene 40 parts Methyl ethyl ketone 40 parts

Next, an adhesive layer coating solution prepared in the composition shown in Tables 1 to 3 below is applied onto the protective layer forming layer by a bar coater so that the film thickness after drying is 1.0 μm. Formed. When the adhesive layer was dried, it was dried with a drier and further allowed to stand in an oven at a temperature of 100 ° C. for 1 minute. The protective layer transfer sheet was obtained by performing the above operations.
In addition, the value in a table | surface shows the weight part of each component. “Resin 1” shown in the following Tables 1 to 3 is a polyester resin having a glass transition temperature of 92 ° C. synthesized by a conventional method from the following acid component and diol component.
(Resin 1)
Acid component: terephthalic acid 50 mol%
Isophthalic acid 50mol%
Diol component: Ethylene glycol 10 mol%
Tetracyclodecane glycol 90 mol%

  The structural formulas of the ultraviolet absorbing copolymers UVA1 to UVA8 and the light stabilizers HALS-A to HALS-E in Tables 1 to 3 are shown below.

[Examples 12 to 15 and Comparative Example 18]
In Examples 12 to 15 and Comparative Example 18, as shown in FIG. 4, the base material 1, the back layer 4 formed on one surface of the base material 1, and the other surface of the base material 1 are formed. And a protective layer forming layer 2. In Examples 12 to 15 and Comparative Example 18, the protective layer forming layer 2 contains an ultraviolet absorbing polymer.

First, a back layer was formed on a substrate in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 17 described above. Next, on the surface of the base sheet opposite to the surface on which the back layer is formed, the protective layer-forming layer coating solution prepared in the compositions shown in Table 4 and Table 5 below is dried by a bar coater and then the film thickness Was applied to form an adhesive layer. When the adhesive layer was dried, it was dried with a drier and further allowed to stand in an oven at a temperature of 100 ° C. for 1 minute. The protective layer transfer sheet was obtained by performing the above operations.
In addition, the value in a table | surface shows the weight part of each component. “BR-87” shown in Tables 4 and 5 below is an acrylic resin (BR-87 manufactured by Mitsubishi Rayon Co., Ltd.).

The structural formulas of the UV-absorbing copolymers UVA1 to UVA8 and the light stabilizers HALS-A to HALS-E in Tables 4 and 5 above are the same as those described above.
[Evaluation]
In order to confirm the performance of the protective layer transfer sheets obtained in Examples 1 to 15 and Comparative Examples 1 to 18, printed materials on which the protective layer was transferred were prepared.
(Y, M, C printing)
First, a thermal transfer image receiving sheet used for a photochelate printer RC602 manufactured by Konica Minolta Photo Imaging and an ink layer ribbon having a thermal diffusible dye were prepared. Next, the receiving layer of the thermal transfer image receiving sheet and the ink layer ribbon are overlapped to face each other, and thermal transfer recording is performed in the order of Y, M, and C using a thermal head under the following conditions to form a gradation image. .

(Y, M, C printing conditions)
-Thermal head-Heating element average resistance: 3195 (Ω)
Printing density in the main scanning direction: 300 dpi Printing density in the sub scanning direction: 300 dpi Applied power: 0.12 (w / dot)
1 line cycle: 5 (msec.)
-Printing start temperature: 40 (° C)
Gradation control method: Using a multi-pulse test printer that can vary the number of divided pulses from 0 to 255 in one line period and having a pulse length obtained by equally dividing one line period into 256. The duty ratio is fixed at 60%, and the number of pulses per line cycle is increased by 0 for 0 steps, 17 for 1 steps, 34 for 2 steps, and 34 from 0 to 255, depending on the gradation. Thus, 16 gradations from 0 step to 15 steps were controlled.

(Protective layer printing)
Next, a protective layer was transferred and formed on the gradation image formed as described above. About the printed matter on which the above thermal transfer recording was performed, the protective layer transfer sheets of Examples and Comparative Examples were overlapped with the protective layer forming layer surface and the image receiving surface facing each other, and the entire print screen was printed by a thermal head under the following printing conditions. A protective layer was formed.

(Protective layer printing conditions)
-Thermal head-Heating element average resistance: 3195 (Ω)
Printing density in the main scanning direction: 300 dpi Printing density in the sub-scanning direction: 300 dpi Printing power: 0.12 (W / dot)
1 line cycle: 5 (msec.)
-Printing start temperature: 40 (° C)
・ Applied pulse: Duty ratio of each divided pulse using a multi-pulse test printer that can vary the number of divided pulses having a pulse length obtained by dividing one line period into 256 equally in a line period from 0 to 255 Was fixed to 70%, the number of pulses per line period was fixed to 200, solid printing was performed, and a protective layer was formed on the entire surface of the receiving layer.

  By the above operation, a printed matter having a protective layer was obtained. In the present invention, light resistance evaluation and color development evaluation were performed on the printed matter.

(Light resistance evaluation)
The conditions for light resistance evaluation are as follows.
・ Irradiation tester: Ci35 manufactured by Atlas
-Light source: Xenon lamp-Filter: Inside = IR filter
Outside = soda lime glass • Black panel temperature: 45 (° C)
Irradiation intensity: measured value at 1.2 (W / m ² ) -420 (nm) Irradiation energy: integrated value at 400 (kJ / m ² ) -420 (nm)

The hue change of the image before and after irradiation under the above light resistance condition is measured with a color difference meter (CR321, manufactured by Konica Minolta Co., Ltd.), and the color difference is calculated by the following formula for a step where the optical reflection density before irradiation is near 1.0. Based on this, the light resistance was evaluated according to the following evaluation criteria.
Color difference ΔE * ab = ((Δa *) ² + (Δb *) ² ) ^1/2
See CIE1976 La * b * color system (JIS Z8729 (1980)) Δa * = a * (after irradiation) -a * (before irradiation)
Δb * = b * (after irradiation)-b * (before irradiation)
(Evaluation criteria for light resistance)
○: Color difference ΔE * ab <5
Δ: 5 ≦ color difference ΔE * ab <10
×: Color difference ΔE * ab ≧ 10
(Color development evaluation)
The printed matter was put in an oven at 110 ° C. for 3 minutes, and the color development was evaluated by measuring the hue change (color difference) before and after that. The method for calculating the color difference is as described above.
(Evaluation criteria for color development)
○: Color difference ΔE * ab <3
×: Color difference ΔE * ab ≧ 3

(Dye contamination)
On the other hand, in order to evaluate the dye contamination of the protective layer transfer sheets obtained in Examples 1 to 15 and Comparative Examples 1 to 18, the following operations were performed.
First, two dye ribbons each including a dye layer containing M dye and a back layer are prepared, and the dye layer of one dye ribbon and the back layer of the other dye ribbon are overlapped to form 20 kg / cm ^2. The sample was further stored for 3 days in an environment of 40 ° C. and 90% RH. Thereby, M dye in a dye layer was moved to the back layer which contacts.
Next, the back layer to which the M dye was transferred and the adhesive layer of the protective layer transfer sheet obtained in Examples and Comparative Examples were superimposed and stored in an environment at 60 ° C. for 2 days. Then, the said back surface layer and the said contact bonding layer were peeled, and it evaluated about the background stain | pollution | contamination of a protective layer. Specifically, it was evaluated by measuring the change in hue (color difference) of the protective layer before and after the adhesive layer was overlaid.
(Evaluation criteria for contamination)
○: Color difference ΔE * ab <3
Δ: 3 ≦ color difference ΔE * ab <5
×: Color difference ΔEab ≧ 5

  Tables 6 and 7 show the results of the light resistance evaluation, the contamination evaluation, and the color development evaluation.

  As is clear from Tables 6 and 7, the protective layer transfer sheets prepared in the examples gave good results in all of the light resistance evaluation, stain resistance evaluation and color development evaluation. On the other hand, the protective layer transfer sheet produced in the comparative example did not give good results in any of light resistance evaluation, contamination evaluation and color development evaluation. Therefore, it was revealed that the protective layer transfer sheet of the present invention is comprehensively excellent in light resistance, stain resistance and color developability.

It is a section schematic diagram showing an example of a protection layer transfer sheet of the present invention. It is a cross-sectional schematic diagram which shows the other example of the protective layer transfer sheet of this invention. It is explanatory drawing explaining the structure of the protective layer transfer sheet in Examples 1-11 and Comparative Examples 1-17. It is explanatory drawing explaining the structure of the protective layer transfer sheet in Examples 12-15 and the comparative example 18. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate 2 ... Layer for protective layer formation 3 ... Back surface layer 4 ... Release layer 5 ... Adhesive layer

Claims (4)

A protective layer that protects the surface of the receptor layer after the thermal diffusible dye is transferred to a thermal transfer image-receiving sheet having a receptor layer containing a metal ion-containing compound capable of reacting with a chelatable thermal diffusible dye A protective layer transfer sheet used for forming,
A substrate and a protective layer forming layer formed on the substrate, wherein the protective layer forming layer has the following general formula (1):

Containing an ultraviolet-absorbing copolymer obtained by copolymerizing an ultraviolet-absorbing monomer represented by an acrylic monomer,
The protective layer transfer sheet, wherein the ultraviolet absorbing copolymer contains 40 mol% or more of the ultraviolet absorbing monomer.   The protective layer transfer sheet according to claim 1, wherein the absorption maximum wavelength of the ultraviolet absorbing copolymer is in the range of 310 to 360 nm.   The protective layer transfer sheet according to claim 1, wherein the protective layer forming layer contains a hindered amine light stabilizer having a molecular weight of 1500 or more.   A printed matter comprising the protective layer transfer sheet according to any one of claims 1 to 3.

Images