JP2007021805A - Thermal transfer image accepting sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal transfer image accepting sheet which can be stored for a long time. <P>SOLUTION: The thermal transfer image accepting sheet comprises a dye accepting layer formed at least on one side of a base sheet, wherein at least one storage stabilizing layer is formed between the base sheet and the dye accepting layer. The storage stabilizing layer preferably contains at least one kind of storage stabilizer selected from the group consisting of an ultraviolet absorber, a photostabilizer and an antioxidant, in the amount of 25 wt.% or more of an aggregate of constituent substances other than the storage stabilizer out of substances constituting the storage stabilizing layer. The ultraviolet absorber is preferably a reactive ultraviolet absorber. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is characterized by a long-term demanded from the market, characterized in that at least one storage stabilization layer is formed between the dye-receiving layer formed on at least one side of the base sheet and the base sheet. The present invention relates to a storable thermal transfer image receiving sheet.

Various thermal transfer methods have been proposed in the past, and a thermal transfer sheet in which a sublimation dye is used as a colorant and supported on a sheet-like base material made of polypropylene or the like, and a thermoplastic resin with good dyeing of the sublimation dye. Among them, a so-called sublimation transfer method using a thermal transfer image receiving sheet in which a dye receiving layer made of a resin or the like is formed on a base sheet such as a plastic film has attracted attention. In this method, a thermal transfer sheet and a thermal transfer image receiving sheet are set facing each other on a printer equipped with a thermal head as a heating means, and three colors of cyan, magenta and yellow or black are obtained by heating from the thermal head for an extremely short time. In this system, the four sublimation dyes added are transferred from the thermal transfer sheet to the thermal transfer image receiving sheet in a dot shape, and a full color image by multicolor dots is reproduced on the thermal transfer image receiving sheet.
Since images obtained by the sublimation transfer method are formed with dyes, exposure to factors that affect the dyes, such as ultraviolet rays and oxidants, cause discoloration, discoloration, etc. faster than images formed with pigments. There is a problem. This problem has been solved by including a storage stabilizer such as an ultraviolet absorber or an antioxidant in the dye-receiving layer of the thermal transfer image-receiving sheet.

  However, such storage stabilizers in the dye-receiving layer often have an undesirable effect on image recording by the sublimation transfer method. For example, in a dye receiving layer to which an ultraviolet absorber is added, properties and functions originally required as a dye receiving layer such as a dyeing property and a film property are deteriorated. In general, an ultraviolet absorber is poorly compatible with a thermoplastic resin, and therefore, when added to a dye receiving layer made of a thermoplastic resin, it tends to bleed out on the surface of the dye receiving layer. As a result, it comes into contact with other objects and is physically removed, volatilized or decomposed by heat, and the effect of adding the same agent becomes temporary. Also, the printed part may bleed due to the bleed-out agent. JP-A-5-212974 (Patent Document 1) proposes that a reactive ultraviolet absorber is contained in the dye-receiving layer. Reactive UV absorbers are UV absorbers that react with and bind to the binder resin and other additives that make up the dye-receiving layer, and are less likely to bleed out than non-reactive UV absorbers, hence thermal transfer image receiving. It is said that the sheet can be stored for a relatively long period of time.

It is generally performed that the additive is added to a layer other than the dye receiving layer, for example, a protective layer provided on the surface side of the dye receiving layer or an intermediate layer provided between the dye receiving layer and the base sheet. Yes. When a protective layer is used, it is generally performed that the protective layer is applied to the surface of the dye receiving layer after the sublimation dye is transferred. As an example using an intermediate layer, Japanese Patent Application Laid-Open No. 5-208562 discloses an image receiving sheet containing a polyvinyl alcohol resin having a specific polymerization degree in an intermediate layer in order to obtain a high-quality recorded image by a sublimation dye. There exists patent document 2). This document discloses that an ultraviolet absorber, an antioxidant and the like are added to the intermediate layer.
JP-A-5-221974 Japanese Patent Laid-Open No. 5-208562

  Even though the reactive ultraviolet absorber has the advantages as described above compared with a normal ultraviolet absorber, it is still poorly compatible with the thermoplastic resin, so that the dye-receiving layer made of the thermoplastic resin has a large amount. Cannot be added. According to Patent Document 1, a reactive ultraviolet absorber can be added to the dye receiving layer only in an amount of about 20% by weight based on the weight of the component forming the dye receiving layer excluding the reactive ultraviolet absorber. Since only a small amount can be added, long-term storage as required by the market has not yet been achieved. Thus, it is generally difficult to find another storage stabilizer that can replace a storage stabilizer having disadvantages in the dye-receiving layer. This problem is not solved at all even in the image receiving sheet for thermal transfer recording disclosed in Patent Document 2 in which an antioxidant, a normal ultraviolet absorber, or the like is added to an intermediate layer containing polyvinyl alcohol resin as an essential component. . This is because the purpose of the image-receiving sheet is to obtain a high-quality recorded image using a sublimation dye, and the intermediate layer contains a specific component in order to achieve the purpose. This is because only an additive which does not adversely affect image recording in the intermediate layer having a thickness is allowed to be added to the intermediate layer.

  This invention was made | formed in view of the said subject, and the solution of the said subject was aimed at by providing a storage stabilization layer between a base material sheet and a dye receiving layer. That is, a component having a function necessary for stably storing the thermal transfer image-receiving sheet for a long time is not provided in the dye-receiving layer, but is provided between the base sheet and the dye-receiving layer as a storage stabilizing layer. It has been found that the above problems can be solved. In particular, ultraviolet absorbers, light stabilizers and antioxidants are suitable as storage stabilizers constituting the storage stabilization layer, and reactive ultraviolet absorbers are suitable as ultraviolet absorbers. I found.

That is, the present invention is a thermal transfer image-receiving sheet in which a dye-receiving layer is formed on at least one side of a substrate sheet, and at least one storage stabilization layer is formed between the substrate sheet and the dye-receiving layer. Is a thermal transfer image-receiving sheet. The storage stabilization layer comprises at least one storage stabilizer selected from the group consisting of an ultraviolet absorber, a light stabilizer and an antioxidant, and a component other than the storage stabilizer that forms the storage stabilization layer ( 25 wt. Of this set of constituent materials other than the component for which the proportion is to be calculated out of the materials constituting the storage stabilization layer, which is the basis for the ratio of the additive amount, is hereinafter referred to as “storage stabilization layer forming component”) It is desirable that it is contained in an amount of% or more.
It is further desirable that the UV absorber is a reactive UV absorber.

(1) Substances such as ozone and water vapor that try to enter the dye receiving layer from the side of the base sheet by providing a storage stabilizing layer containing a storage stabilizer between the base sheet and the dye receiving layer. Incident light and conducted heat (hereinafter referred to as “invasion factor”) can be prevented by the storage stabilization layer. In addition, for the invasion factor to the dye receiving layer from the side not in contact with the storage stabilizing layer (hereinafter referred to as “surface side”), the storage stabilizing layer absorbs the invasion factor that has passed through the dye receiving layer. By capturing, it is possible to reduce the return amount of the invasion factor to the dye receiving layer due to diffusion from the storage stabilization layer to the dye receiving layer or reflection from the base sheet. As a result, it is not necessary to add a storage stabilizer to the dye-receiving layer at all, or a necessary minimum addition amount that does not impair the properties of the dye-receiving layer is sufficient, and the original properties and functions of the dye-receiving layer are deteriorated. Storage stability is improved without any problems. Note that the storage stabilizing layer of the present invention provided on the side opposite to the surface side is naturally against the invasion factor that has penetrated from the surface side but does not pass through and remains in the dye receiving layer and acts directly on the dye receiving layer. However, there is no effect.

(2) Phenomenon that fades for a long time under the influence of ozone, water vapor or heat even when stored in a dark place such as an album by providing a storage stabilizing layer on the base sheet side of the dye receiving layer Is also effective.

(3) The storage stabilizer contained in the dye-receiving layer is unnecessary or the amount thereof can be reduced, so that the transparency of the dye-receiving layer is simply improved by reducing the amount of the additive, and the storage stabilizer in the dye-receiving layer is improved. In particular, the yellowing, browning, etc. of the UV absorber with time are eliminated or reduced. Thus, although the opacity of the storage stabilization layer is increased, the transparency of the dye-receiving layer is improved and the clarity of the recorded image is improved.

(4) Even if a storage stabilizer such as a UV absorber introduced in a large amount in the storage stabilization layer bleeds out, it gradually occurs, so that the transfer of the same agent to the dye receiving layer occurs slowly. Therefore, storage stability can be achieved in the long term.

Below, the specific suitable example of the component of this invention is given.
The storage stabilization layer of the present invention may be based on a resin that is usually used as the main component of the intermediate layer of the thermal transfer image-receiving sheet.

  As described above, the storage stabilization layer preferably contains at least one storage stabilizer that is an ultraviolet absorber, a light stabilizer, or an antioxidant. More preferably, the UV absorber is a reactive UV absorber.

  The storage stabilizer may contain an antiaging agent.

  The storage stabilizer is preferably contained in the storage stabilizer in an amount of 25% by weight or more of the storage stabilization layer forming component. If it is less than 25% by weight, the required storage stability may not be obtained. The upper limit of the amount of the storage stabilizer to be contained in the storage stabilization layer is 90% by weight or less, more preferably 80% by weight of the component for forming the storage stabilization layer in consideration of adhesion to other materials such as a base sheet. % Or less is preferred. In the present invention, since the storage stabilization layer is not a layer exposed on the surface, the storage stabilizer is a resin constituting the storage stabilization layer (hereinafter referred to as “storage stabilization layer host resin” in the present specification). And may be contained in the storage stabilization layer in a state that is not compatible with each other. Therefore, a large amount of storage stabilizer can be contained in the storage stabilization layer.

The amount of the storage stabilization layer applied to the substrate sheet is appropriately determined according to the amount of the storage stabilizer in the storage stabilization layer and the desired storage stability, but is 0.1 g / m ² or more 6 preferably .0g / m ² or less, more preferably 0.5 g / m ² or more 2.0 g / m ² or less. If it is less than the lower limit of the range, the desired storage stability may not be obtained, and if it exceeds the upper limit of the range, the image density may be deteriorated.

  In the present invention, the storage stabilization layer does not have to be a single layer, and may be composed of a plurality of layers such as a layer responsible for UV resistance and a layer responsible for dark fading resistance. In that case, the total amount of the storage stabilizer contained in each layer constituting the storage stabilization layer needs to be 25% by weight or more of the total of each storage stabilization layer forming component. The dye receiving layer in the present invention may be composed of a conventional binder resin that constitutes the dye receiving layer of the thermal transfer image receiving sheet.

  If the thermal transfer image-receiving sheet of the present invention does not extremely impair the effects of the present invention, such as not allowing ultraviolet light to pass between the dye-receiving layer and the storage stabilizing layer, the back surface layer, the surface layer, the intermediate layer, and the like Layers may be provided as needed.

Ａは直接結合するか置換基を有していてもよいメチレン基、アルキレン基、−Ｏ−、
−ＮＨ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、を示す。Ｒ１、Ｒ２は水酸基、ヒドロキシアルキル基を示す。Ｒ３、Ｒ４は水素原子、アルキル基、アルコキシル基、アリール基、ハロゲン原子を示す。

ＲはＨ又はＣＨ_３、Ａは−ＯＣＨ_２ＣＨ_２−又は−ＣＨ_２ＣＨ(OH)ＣＨ_２−を示す。

ＲはＨ又はＣＨ_３、Ａは−ＣＨ_２ＣＨ_２−又は−ＣＨ_２ＣＨ(OH)ＣＨ_２−
を表す。
これらの紫外線吸収剤は単独でも二種以上を混合しても使用することができる。 Examples of ultraviolet absorbers constituting the storage stabilizer according to the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyl Oxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 1,4'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy 2'-carboxybenzophenone, 2-hydroxy-4-oxybenzylbenzophenone, 2-hydroxy-4-chlorobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxy-4'- Benzophenone UV absorbers such as methylbenzophenone, 2- (2'-hydroxy-5'-methylphenone) benzotriazole, 2- (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-4' -Octoxy) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-(1-methyl-1) -Phenylethyl) -5 '-(1,1,3,3-tetramethylbutyl)) benzotriazole and other benzotriazole ultraviolet absorbers, phenyl salicylate, P-octylphenyl salicylate, P-t-butylphenyl salicylate, Salicylic acid phenyl ester ultraviolet absorbers such as carboxylphenyl salicylate and methylphenyl salicylate, and addition-polymerizable double bonds, alcoholic hydroxyl groups, epoxy groups, amino groups, to conventionally known non-reactive ultraviolet absorbers, Carboxyl groups, reactive UV absorbers and reactive group was introduced by a conventional introduction method, such as an isocyanate group. Examples of reactive ultraviolet absorbers are shown in general formulas (I) to (III).

A is a methylene group, an alkylene group, -O-, which may be directly bonded or have a substituent.
-NH -, - S -, - SO -, - SO 2 -, shows the. R1 and R2 each represent a hydroxyl group or a hydroxyalkyl group. R3 and R4 represent a hydrogen atom, an alkyl group, an alkoxyl group, an aryl group, or a halogen atom.

R represents H or CH ₃ , and A represents —OCH ₂ CH ₂ — or —CH ₂ CH (OH) CH ₂ —.

R is H or CH ₃ , A is —CH ₂ CH ₂ — or —CH ₂ CH (OH) CH ₂ —
Represents.
These ultraviolet absorbers can be used alone or in combination of two or more.

Reactive UV absorbers can be reactively fixed to a substrate such as a resin that constitutes a storage stabilization layer by using various types of electrons such as resonant transformer type, insulated core transformer type, high frequency type, dynamitron type, and linear type. Known techniques can be used as they are, such as irradiating an electron beam emitted from a line accelerator, irradiating ultraviolet rays emitted from a light source such as a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc, or a metal hydride lamp. The electron beam irradiation condition is 30 to 1500 keV, preferably 100 to 300 keV, and the ultraviolet light irradiation condition is 100 to 2500 mJ / cm ² , preferably 500 to 1800 mJ / cm ² in terms of the integrated light amount. Since it varies depending on the pigment and other additives added to the stabilization layer, it should be determined appropriately.

  Examples of antioxidants and antioxidants constituting the storage stabilizer according to the present invention include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, Styrenated phenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-isopropylidenebisphenol, 2,6-bis (2'-hydroxy-3'-t-butyl-5) '-Methylbenzyl) -4-methylphenol, 4,4'-thiobis- (3-methyl-6-tert-butylphenol), tetrakis- {methylene (3,5-di-tert-butyl-4-hydroxyhydrocinna Mate)} methane, parahydroxyphenyl-3-naphthylamine, 2,2,4-trimethyl-1,2-dihydroquinoline, thiobis (β-naphthol), mel Ptobenzothiazole, mercaptobenzimidazole, aldol-2-naphthylamine, bis (2,2,6,6-tetramethyl-4-piperidyl) separate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, dilauryl -3,3'thiodipropionate, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl-3,3'-thiodibrominate, tris (4-nonylphenol) ) Phosphite. These antioxidants and antioxidants can be used alone or in combination of two or more.

  Examples of the light stabilizer constituting the storage stabilizer include hindered amine light stabilizers. Specifically, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sankyo: SANOL LS770), bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) Sebacate (Sankyo LS765), 1- {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (SANKYO: SANOL LS2626), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (Sankyo: SANOL LS744), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] deca -2,4-dione (Sankyo LS440), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6, 6-pentamethyl-4-piperidyl) (manufactured by Ciba-Geigy: TINUVIN 144), bis (2,2,6,6-tetramethyl-4-piperidinyl) succinate (manufactured by Ciba-Geigy: TINUVIN 780FF), dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (manufactured by Ciba Geigy: TINUVIN 622LD), poly {[6- (1,1,3,3-tetramethyl Butyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hex Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (Ciba Geigy: CHIMASSORB 944LD), N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N -Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine polycondensate (manufactured by Ciba Geigy: CHIMASSORB 119FL), HA- 70G (manufactured by Sankyo), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68, ADK STAB LA-82, ADK STAB LA-87 (all Asahi Denka) (Made by industry) etc. are mentioned.

  These hindered amine light stabilizers can be used singly or in combination of two or more, but considering the effect of improving light resistance, it is preferable to use them together with the aforementioned ultraviolet absorber.

  Examples of resins constituting the storage stabilization layer include polyester resins, polyolefin resins, polystyrene resins, polyamide resins, halogenated polymers, vinyl polymers, cellulose resins, polyvinyl acetal resins, olefins and other vinyl monomers. Copolymer resins, polycarbonate resins, and polyurethane resins, and polyurethane resins are preferred from the viewpoint of adhesion to the substrate. When a reactive ultraviolet absorber is used as the ultraviolet absorber, an addition polymerizable monomer or oligomer is preferably added as necessary. Examples of such monomers and oligomers include monofunctional (meth) acrylate monomers, polyfunctional (meth) acrylate monomers, and polyfunctional (meth) acrylate oligomers. These (meth) acrylate compounds can be used individually by 1 type, or may use 2 or more types together.

  Specific examples of monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, glycerol (meta Acrylate, glycidyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified Tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate , Trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, benzyl (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) Acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol / poly Propylene glycol (meth) acrylate, alicyclic modified neopentyl glycol (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified butoxylated phosphoric acid (meth) acrylate, ethylene oxide modified phenoxylated phosphoric acid (meth) acrylate, Trimethoxysilylpropyl (meth) acrylate, sodium ethyl sulfonate (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, morpholine (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) ) Acrylate, ethylene oxide modified phthalic acid (meth) acrylate, propylene oxide modified phthalic acid (meth) acrylate, ( Data) acrylic acid amide, (meth) acrylic acid N, N'-dimethylaminoethyl, and (meth) acrylic acid.

  Among these monofunctional (meth) acrylate monomers, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid amide, glycidyl (meth) acrylate, methyl (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be preferably used.

  Specific examples of the polyfunctional (meth) acrylate monomer include bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, and ethylene oxide modified bisphenol F di (meth). Acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, glycerol di ( (Meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate 1,4-butanediol di (meth) acrylate, epichlorohydrin modified 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified-1,6-hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate eopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide Modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane Li (meth) acrylate, neopentyl glycol modified trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetratrimethylolpropane tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) Acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) a Chryrate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di ( (Meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, caprolactone modified phosphoric acid di (meth) acrylate, epichlorohydrin modified di (meth) acrylate, tris {(meth) acryloyl Oxyethyl} isocyanurate, caprolactone-modified tris {(meth) acryloyloxyethyl} isocyanate Cyanurate, zinc (meth) acrylate. Further, phosphazene compounds having a (meth) acryloyloxy group such as hexa {(meth) acryloyloxyethoxy} cyclotriphosphazene and octa {(meth) acryloyloxyethoxy} cyclotetraphosphazene can be given. These may be acrylate / methacrylate mixtures such as glycerol (meth) acrylate.

  Among these polyfunctional (meth) acrylate monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like can be preferably used.

  As the polyfunctional (meth) acrylate oligomer, a polyfunctional polyester (meth) acrylate oligomer, polyfunctional urethane (meth) acrylate oligomer, polyfunctional epoxy (meta) having at least two (meth) acryloyloxy groups in one molecule. ) Acrylate oligomer, polyfunctional ether (meth) acrylate oligomer, and the like. As these oligomers, those produced from aliphatic or alicyclic compounds can be preferably used for improving weather resistance. Specific examples of these oligomers are listed below. Specific examples of the polyfunctional polyester (meth) acrylate oligomer include compounds synthesized from (meth) acrylic acid, polyhydric alcohols, and polybasic acids (anhydrides). Specific examples of the polyhydric alcohol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, dimethylol. Examples include heptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and glycerin. Specific examples of polybasic acids (anhydrides) are malonic acid, (anhydrous) succinic acid, alkenyl succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, isosebacic acid, (anhydrous) maleic acid Acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, and (anhydrous) trimellitic acid.

  Examples of the polyfunctional urethane (meth) acrylate oligomer include compounds obtained by reaction of polyisocyanate, polyol and hydroxy (meth) acrylate.

  Specific examples of the polyisocyanate include hydrogenation of hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and aromatic isocyanate. Diisocyanates (such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, etc.), triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, and the like. -Polyisocyanate obtained by increasing the amount of isocyanate. Specific examples of the polyol include aliphatic, alicyclic and aromatic polyols, polyester polyols and polyether polyols. Specific examples of aliphatic and alicyclic polyols and polyether polyols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, Polypropylene glycol, neopentyl glycol, dimethylol heptane, dimethylol propionic acid, dimethylol butyric acid, trimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, glycerin, hydrogenated bisphenol A, etc. It is done. Examples of the aromatic polyol include ethoxylated bisphenol A and ethoxylated bisphenol S. Specific examples of the polyester polyol include caprolactone-modified diol.

Specific examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol di (meth) acrylate, glycerol (meth) acrylate, And pentaerythritol tri (meth) acrylate.
Examples of the polyfunctional epoxy (meth) acrylate oligomer include compounds obtained by addition reaction of polyglycidyl ether and (meth) acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

  Examples of the polyfunctional ether (meth) acrylate oligomer include compounds obtained by transesterification of a polyether obtained by reacting a polyol with ethylene oxide or propylene oxide, and ethyl (meth) acrylate. Specific examples of the polyol here include glycerin and hexanetriol.

  The material for the base sheet is not particularly limited as long as it can be used as the base sheet for the sublimation image-receiving sheet. Examples thereof include high-quality paper, art paper, coated paper, cast-coated paper, synthetic resin-impregnated paper, paper such as synthetic paper, and various plastic sheets such as polyolefin, polyethylene terephthalate, polystyrene, and polycarbonate. In addition, a foamed sheet formed by adding a white pigment or various fillers to the synthetic resin used for these materials, an opaque sheet, or a composite sheet of any combination thereof can be used.

  The thickness of the base sheet is not particularly limited, but a thickness of about 10 to 300 μm is generally used.

Examples of binder resins for the dye-receiving layer include polyester resins, polyolefin resins, polystyrene resins, polyamide resins, halogenated polymers, vinyl polymers, cellulose resins, polyvinyl acetal resins, olefins and other vinyl monomers. And copolymer resins and polycarbonate resins.

  For the dye-receiving layer, a release agent for imparting releasability with the thermal transfer sheet, for example, silicone oil, fluorosurfactant, phosphate ester, etc., within a range not departing from the object of the present invention. Reactive ultraviolet absorbers, reactive ultraviolet absorbers, antioxidants, pigments such as titanium oxide, calcium carbonate, and fine powder silica, fillers, and the like can be added.

  In the description of the following experimental examples, “parts” means all parts by weight.

− Preparation of thermal transfer image-receiving sheet −
[Create base sheet]
On the coated paper (A-2, manufactured by Mitsubishi Paper Industries, thickness 165 μm), a urethane adhesive was applied at a coating amount of 5 g / m ² , and an unstretched polypropylene film (Byron Film-CTP1128, manufactured by Toyobo, 30 μm thick) was laminated by dry lamination to obtain a substrate sheet.

[Formation of storage stabilization layer]
The following composition was mixed and the resin component was dissolved to prepare a coating solution for forming a storage stabilization layer consisting of a uniform solution.
Urethane resin (Rezamin 8883HV, manufactured by Dainichi Seika) 10 parts stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Specialty Chemicals) 2 parts 2- ( 2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (2- (2H-Benzotriazol-2-yl) ) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol) (Tinuvin 928, manufactured by Ciba Specialty Chemicals) 4 parts bis (2,2,6,6) -Tetramethyl-4-piperidinyl) sebacate ([bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate]) (Tinuvin 770DF, manufactured by Ciba Specialty Chemicals) 1 part Toluene 50 parts Isopropyl alcohol 50 parts Protected The coating solution for forming a stable layer was applied on a base sheet with a Mayer bar so that the coating amount after drying was 0.5 g / m ^2, and dried to form a storage stabilization layer.

[Formation of dye receiving layer]
The following composition was mixed and the resin component was dissolved to prepare a coating solution for forming a dye-receiving layer consisting of a uniform solution.
10 parts of polyester resin (Byron 200, manufactured by Toyobo)
90 parts of a mixture of methyl ethyl ketone: toluene = 1: 1 The obtained dye-receiving layer-forming coating solution is stored on a stabilizing bar with a Mayer bar on the storage stabilization layer so that the coating amount after drying is 5.0 g / m ^2. The dye receiving layer was formed by coating and drying.
Thus, a thermal transfer image receiving sheet was obtained.

− Preparation of thermal transfer image-receiving sheet −
[Create base sheet]
A base sheet was prepared in the same manner as in Example 1.

[Formation of storage stabilization layer]
The following composition is mixed and the resin component is dissolved to form a first storage stabilization layer (hereinafter referred to as “first storage stabilization layer” in this embodiment) consisting of a uniform solution. A coating solution was prepared.
Styrene butadiene latex (Nipol Latex LX430, manufactured by Nippon Zeon)
10 parts stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Specialty Chemicals) 3 parts water 100 parts isopropyl alcohol 10 parts The first storage stabilization layer was formed by coating the coating liquid for forming a chemical layer with a Mayer bar and drying it in the form of a base sheet so that the coating amount after drying was 0.2 g / m ² .

In order to form the second storage stabilization layer (hereinafter referred to as “second storage stabilization layer” in the present example) consisting of a uniform solution by mixing the following composition and dissolving the resin component: A coating solution was prepared.
Styrene butadiene latex (Nipol Latex LX430, manufactured by Nippon Zeon)
10 parts acrylic resin component: benzotriazole-based reactive ultraviolet absorber component = 7: 3 (weight ratio) mixture (ULS-1383MG manufactured by Yushi Kogyo Co., Ltd.) 24 parts 1-hydroxy-cyclohexyl-phenyl-ketone (ultraviolet polymerization initiation) Agent) (Irgacure 184, manufactured by Ciba Specialty Chemicals) 2 parts water 150 parts isopropyl alcohol 15 parts

((Note) In the second storage stabilization layer of Example 2, the weight part of the reactive ultraviolet absorber is 24 × (3 / (7 + 3)) = 7.2 parts by weight. The stable layer forming component is 10 parts of styrene butadiene latex as a host resin + (24 parts of ultraviolet absorber mixture-7.2 parts of reactive ultraviolet absorber) +2 parts of ultraviolet polymerization initiator = 28.8 parts. The ratio of the reactive ultraviolet absorber is (7.2 / 28.8) × 100 = 25% by weight.)
The obtained second storage stabilization layer forming coating solution is coated with a Mayer bar on the first storage stabilization layer so that the coating amount after drying is 0.4 g / m ² , It dried and irradiated with the ultraviolet-ray with the metal hydride lamp, and formed the 2nd storage stabilization layer.

[Formation of dye receiving layer]
A dye-receiving layer was formed on the second storage stabilization layer in the same manner as in Example 1.
Thus, a thermal transfer image receiving sheet was obtained.

− Preparation of thermal transfer image-receiving sheet −
First and second storage stabilization in the same manner as in Example 2 except that 2 parts of light stabilizer TINUVIN 770DF was added to the composition of the second storage stabilization layer forming coating solution of Example 2. A thermal transfer image-receiving sheet having a layer was prepared.

− Preparation of thermal transfer image-receiving sheet −
[Create base sheet]
A base sheet was prepared in the same manner as in Example 1.

[Formation of storage stabilization layer]
The following composition was mixed and the resin component was dissolved to prepare a coating solution for forming a storage stabilization layer consisting of a uniform solution.
Polyester resin (pylon 200, manufactured by Toyobo) 10 parts
A compound of general formula (I) in which A is a methylene group, R1 and R2 are hydroxyl groups, and R3 and R4 are hydrogen atoms. 4 parts stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ( Irganox 1076) 2 parts 1-hydroxy-cyclohexyl-phenyl-ketone (UV polymerization initiator) (Irgacure 183, manufactured by Ciba Specialty Chemicals) 1.5 parts 100 parts mixture of methyl ethyl ketone: toluene = 1: 1 The stabilizing layer forming coating solution was coated on a base sheet with a Mayer bar so that the coating amount after drying was 0.7 g / m ² and dried. Then, the storage stabilization layer was formed by irradiating ultraviolet rays with a metal hydride lamp.

[Formation of dye receiving layer]
On the storage stabilization layer, a dye receiving layer was formed in the same manner as in Example 1.
Thus, a thermal transfer image receiving sheet was obtained.

Comparative Example 1-Preparation of thermal transfer image receiving sheet-
A thermal transfer image-receiving sheet was obtained in the same manner as in Example 1 except that the storage stabilization layer was not formed.

Comparative Example 2-Preparation of thermal transfer image receiving sheet-
A thermal transfer image receiving sheet was obtained in the same manner as in Comparative Example 1 except that the composition of the dye receiving layer forming coating solution was changed to the following composition.
Polyester resin (pylon 200) 10 parts 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (Tinubin 928)
90 parts of 2 parts methyl ethyl ketone: toluene = 1: 1 mixture

Comparative Example 3-Preparation of thermal transfer image receiving sheet-
A thermal transfer image receiving sheet was obtained in the same manner as in Example 1 except that the composition of the storage stabilizing layer forming coating solution was changed to the following composition.
Urethane resin (Rezamin 8883HV, manufactured by Dainichi Seika) 10 parts stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Specialty Chemicals) 1 part 2- ( 2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (Tinuvin 928, manufactured by Ciba Specialty Chemicals) 0 0.5 part bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (manufactured by Tinuvin 770DF Ciba Specialty Chemicals) 0.5 part toluene 50 parts isopropyl alcohol 50 parts

− Creating print samples −
The thermal transfer image-receiving sheets obtained in the examples and comparative examples were cut into a size of 100 × 140 mm. Sublimation type thermal transfer printer CVP-G7 (product name, manufactured by Sony) is set with the sublimation type thermal transfer ribbon for the printer, and the reflection density (measured with Macbeth densitometer RD914 (product name) manufactured by Gretag Macbeth) is approximately 1.0. Two print samples were prepared for each example and comparative example while adjusting so that

− Evaluation test −
The obtained print sample was subjected to a light resistance test and a dark fading resistance test as follows. The results are shown in Table 1.

[Light resistance test]
One of the obtained print samples was exposed for 48 hours using a xenon long life fade meter (Spectrolino, manufactured by Shimadzu Corporation), and the reflection density before and after exposure was measured using a Macbeth densitometer (RD914, manufactured by Gretag Macbeth).
Light resistance is the following formula

Concentration remaining rate (%) = (reflection density after exposure / reflection density before exposure) × 100

The concentration residual ratio (%) calculated by As the numerical value is closer to 100%, the density change is smaller, that is, the light resistance is better, and as the numerical value is closer to 0%, the density change is larger, that is, the light resistance is worse.

[Dark fade resistance test]
The remaining one of the print samples was left in a dark place at a temperature of 60 ° C. and a humidity of 60 ° C. for 7 days, and the reflection density before and after being left was measured with a Macbeth densitometer (RD914 Gretag Macbeth).
The dark blue color is

Density remaining rate (%) = (reflected density after being left / reflected density before being left) × 100

The concentration residual ratio (%) calculated by As the numerical value is closer to 100%, the density change is smaller, that is, the dark fading property is better, and as the numerical value is closer to 0%, the density change is larger, that is, the dark fading property is worse.

耐光性、耐暗褪色性とも残存率が８０％以上；◎
７０〜８０％：○
７０％未満：×とする。

Residual rate of light resistance and dark fading resistance is 80% or more;
70-80%: ○
Less than 70%: x.

Claims (3)

  A thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one side of a substrate sheet, wherein at least one storage stabilization layer is formed between the substrate sheet and the dye-receiving layer. Thermal transfer image receiving sheet.   The storage stabilization layer may include at least one storage stabilizer selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant, and a material other than the storage stabilizer among the substances constituting the storage stabilization layer. The thermal transfer image-receiving sheet according to claim 1, wherein the thermal transfer image-receiving sheet is contained in an amount of 25% by weight or more of the aggregate of the constituent materials. The thermal transfer image-receiving sheet according to claim 1 or 2, wherein the ultraviolet absorber is a reactive ultraviolet absorber.