JP4238184B2 - Thermal transfer recording material and thermal transfer recording method - Google Patents

Description

  The present invention relates to a thermal transfer recording material and a thermal transfer recording method. More specifically, the present invention relates to a thermal transfer recording material for obtaining an image having high density, high sensitivity and good fixability, and high density using the thermal transfer recording material. The present invention relates to a thermal transfer recording method capable of recording an image with high sensitivity.

Conventionally, as a method for obtaining a color hard copy, a color image recording technique has been studied by inkjet, electrophotography, thermal transfer, silver halide photosensitive material, and the like. Of these, the thermal transfer recording material, in particular, has advantages such as easy operation and maintenance, downsizing and cost reduction of the apparatus, and low running cost.
By the way, in the thermal transfer recording material of the thermal transfer system, the dye used for this recording material is important. Patent Document 1 describes a heat-sensitive transfer recording material having a good maximum density, but has a problem that the stability of the obtained image, in particular, fixing property and light resistance are inferior.

  On the other hand, thermal transfer recording materials and image forming methods using heat diffusible dyes (hereinafter referred to as post-chelate dyes) that can be chelated for the purpose of improving these have been proposed. ing. The images formed by using post-chelating dyes disclosed in Patent Documents 2 to 4 are excellent in light resistance and fixability, but are sufficient in terms of the sensitivity of the thermal transfer recording material and the storage stability of the material itself. There was a need for further improvement rather than satisfaction.

  Further, the post-chelate dyes disclosed in Patent Documents 2 to 4 and the like form bidentate or tridentate chelate dyes, and azophores of chromophores as groups that coordinate to metal ions. A group is used. In thermal transfer recording using these dyes, there is a large hue difference between the chelate dye and the chelate dye, so that when the chelate reaction is insufficient during image formation, absorption of unreacted chelate dye remains. In order to obtain a full color image due to irregular absorption of the formed chelate dye itself, further improvement in color reproduction is desired.

On the other hand, Patent Document 5 discloses an example using a dye that does not use an azo group, and an improvement can be seen in the above color reproduction, but the maximum density and sensitivity are insufficient, and further improvements are made. Was desired.
US Pat. No. 4,757,046 JP 59-78893 A JP 59-109349 A Japanese Unexamined Patent Publication No. 60-2398 JP-A-9-123620

  An object of the present invention is to provide a thermal transfer recording material for obtaining an image having high density, high sensitivity, and good fixability, and a thermal transfer recording method using the recording material.

The object of the present invention is achieved by the following constitution.
1. A thermal transfer recording material comprising a dye represented by the following general formula (2) .

[Wherein, R ₉ and R ₁₀ represent a methyl group . ]

2 . The heat-sensitive transfer recording material having a dye-donor layer containing the color-containing represented by the general formula on a support (2), overlapping the image-receiving material is heated in accordance with sensitive transfer recording material to the image information, wherein A thermal transfer recording method comprising forming an image on an image receiving material.

〔式中、Ｒ _１ は置換基を表し、Ｒ _２ はアルキル基、アルケニル基、アルキニル基またはシクロアルキル基を表し、Ｒ _３ 及びＲ _４ は水素原子または置換基を表し、Ｒ _５ 、Ｒ _６ 、Ｒ _７ 及びＲ _８ は水素原子、アルキル基またはアリール基を表す。Ｚは５又は６員の含窒素複素環を形成するために必要な非金属原子群を表す。〕 3 . The heat-sensitive transfer recording material having a dye-donor layer containing the color-containing represented by the general formula on a support (2), overlapping the image receiving material having a dye image-receiving layer containing a metal ion-containing compound on a support, A thermal transfer recording method, wherein the thermal transfer recording material is heated according to image information, and a metal chelate dye image is formed on the image receiving material by a reaction between the dye and the metal ion-containing compound.
The following (1) is mentioned as a reference invention of the present invention.
(1) A thermal transfer recording material comprising at least one dye represented by the following general formula (1).

[Wherein R ₁ represents a substituent, R ₂ represents an alkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group, R ₃ and R ₄ represent a hydrogen atom or a substituent, R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group. Z represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. ]

  The heat-sensitive transfer recording material of the present invention basically has a dye-donating layer containing a dye that becomes mobile by heat and a binder on a support. This dye-donating layer prepares a coating liquid by dissolving or dispersing a dye that becomes mobile by a conventionally known heat and a binder resin in an appropriate solvent, and this is used for a conventionally known thermal transfer dye-donating material. It is formed on one surface of the support by coating and drying. The dye-donating layer may be formed in a single layer, but may be formed in a structure of two or more layers, for example, when a method of repeatedly using a dye is used. In this case, the dye content and the dye / binder ratio in each layer may be different.

The image receiving material of the present invention means a dye image receiving material for thermal transfer recording, and receives an image of a dye transferred by heat from a dye donating layer. Basically, an image receiving layer is laminated on a support.
The image receiving layer of the present invention can be formed of a support, an image receiving layer binder, and various additives.

According to the present invention, it is possible to obtain a thermal transfer recording material and a thermal transfer recording method that give an image having high density, high sensitivity, and good fixability. And among the pigment | dyes (reference invention) represented by General formula (1), according to the pigment | dye (pigment of this invention) represented by General formula (2) , the effect is more remarkable.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

First, the dye represented by the general formula (1) according to the reference invention of the present invention will be described in detail.
In the general formula (1), R ₁ represents a substituent.

The substituent represented by R ₁ is not particularly limited, and examples thereof include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group). 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 groups (eg, methylthio group, ethylthio group, etc.), arylthio groups (eg, phenylthio group, naphthylthio group, etc.), alkenyl groups (eg, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group) 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexyl group Senyl groups, etc.), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), alkynyl groups (eg, propargyl groups, etc.), heterocyclic groups (eg, pyridyl groups, thiazolyl groups, oxazolyl groups, imidazolyl groups, 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, etc.), phosphono group, acyl group (acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexane) Silaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl) 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 groups (eg methoxy group, ethoxy group, propoxy group etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), heterocyclic oxy groups, siloxy An acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, Cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (eg, 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, etc.), alkoxycarbonylamino group (example For example, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), heterocyclic thio group , Thioureido groups, carboxyl groups, carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups, and the like.

  These substituents may be further substituted with the same substituent.

The R _1, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, an alkoxy group, an amino group, and an alkoxycarbonyl group are preferable, an alkyl group is particularly preferred.
In the general formula (1), R ₂ 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 ₂ include the same groups as the alkyl group, alkenyl group, alkynyl group or cycloalkyl group in R ₁ .

The alkyl group, alkenyl group, alkynyl group or cycloalkyl group represented by R ₂ may be substituted with the same substituent as the substituent represented by R ₁ .
R ₂ is preferably an alkyl group.

In general formula (1), _{R 3} and _{R 4} represents a hydrogen atom or a substituent. Examples of the substituent represented by R ₃ and R ₄ include the same groups as the substituent represented by R ₁ , and these substituents may be further substituted with the same substituent.
As R ₃ and R ₄ , a hydrogen atom, an alkyl group, and an aryl group are preferable, and a hydrogen atom is particularly preferable.

In the general formula (1), R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group. Examples of the alkyl group and aryl group represented by R ₅ , R ₆ , R ₇ and R ₈ include the same groups as the alkyl group and aryl group in R ₁ .

The alkyl group and aryl group represented by R ₅ , R ₆ , R ₇ and R ₈ may be substituted with the same substituent as the substituent represented by R ₁ .
R ₅ , R ₆ , R ₇ and R ₈ are preferably hydrogen atoms.

  In the general formula (1), Z represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

Specific examples of the heterocyclic ring include pyridine ring, pyrazole ring, imidazole ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, oxazole ring, quinoline ring, benzothiazole ring, and benzoxazole ring. it can. 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 ₁ .

Hereinafter, the coloring matter of the present invention will be described.

In the general formula (2), R ₉ is a methyl group .
In the general formula _{(2), R 10} is a methyl group.

Hereinafter, although the specific example of the pigment | dye represented by the said General formula (1) and General formula (2) is shown, this invention is not limited by the following specific examples. However, the dye of the present invention is limited to the following exemplified dye 1, and the other exemplified dyes 2 to 41 are reference dyes.

Below, the synthesis example of the pigment | dye represented by General formula (2) is shown.

  20.0 g of compound AA, 8.6 g of compound AB and 10 g of triethylamine were added to 200 ml of ethanol, and the mixture was reacted for 1 hour with heating under reflux. After completion of the reaction, ethanol was removed under reduced pressure, and then the resulting residue was crystallized by adding ethyl acetate. The precipitated crystals were filtered, washed with ethyl acetate and water, and dried to obtain 13.8 g of a yellow solid.

  The analysis result of the obtained solid by 1H-NMR is as follows, and it was confirmed to be an exemplified dye. The yield was 94%.

1H-NMR (400 MHz, deuterated dimethyl sulfoxide, δ (ppm)): 2.15 (s, 3H), 3.18 (s, 3H), 3.41 (t, 2H), 4.10 (t , 2H), 7.05 (d, 1H), 7.11 (m, 1H), 7.22 (d, 1H), 7.77 (m, 1H), 8.06 (dd, 1H), 8 .36 (dd, 1H)
The absorption maximum of the obtained dye in the acetone solution was 439 nm.

Hereinafter, the thermal transfer recording material (hereinafter also referred to as a thermal transfer sheet) of the present invention will be described.
(Support)
The support used for the heat-sensitive transfer recording material of the present invention can be the same support used for conventional thermal transfer sheets without any particular limitation, and is not particularly limited. Specific examples of preferred supports include thin papers such as glassine paper, condenser paper, and paraffin paper, polyethylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polyether ketone, polyether sulfone and other highly heat-resistant polyesters, polypropylene, and 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.

  The thickness of the support can be appropriately selected depending on the material so that the strength, thermal conductivity, heat resistance and the like are appropriate, but usually a thickness of about 1 to 100 μm is preferably used.

  When the support as described above has poor adhesion to a dye-donating layer (hereinafter also referred to as a thermal transfer layer or an ink layer) formed on this surface, the surface can be subjected to primer treatment or corona treatment. preferable.

(Ink layer)
In the present invention, as the heat diffusible ink to be contained in the ink layer provided on one surface of the support, at least one dye represented by the general formula (2) of the present invention is used.

The addition amount of the dye used in the present invention is usually preferably from 0.05 g to 20 g, more preferably from 0.1 g to 5 g, based on 1 m ^{2 of} the ink layer described later.

(binder)
The binder resin used for the ink layer is a water-soluble polymer such as cellulose, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, polyvinyl. There are polymers soluble in organic solvents such as acetal, ethyl cellulose, nitrocellulose and the like. Among these resins, polyvinyl butyral, polyvinyl acetal or cellulose resin having excellent storage stability is preferable. When using a polymer that is soluble in an organic solvent, one or more polymers may be used in the form of a latex dispersion in addition to being used by dissolving them in an organic solvent. The amount of the binder resin used is preferably 0.1 g to 50 g per 1 m ² of the support.

  In order to improve the releasability with the dye image-receiving layer (hereinafter also referred to as the dye image-receiving layer), a release agent may be added or a separate release layer containing the release agent may be provided. Good. As the release agent, reactive curable silicones, phosphate ester surfactants, fluorine compounds, and the like can be used. As for the usage-amount of a mold release agent, 0.5-40 mass% is preferable with respect to solid content of the layer to contain. When providing a release layer, the same binder as that used for the ink layer can be used.

(BC layer: also referred to as a back coat layer, a back coat layer, a back layer, an anti-sticking layer, etc.)
It is preferable to provide a BC layer for imparting heat resistance and stable running property of the thermal transfer sheet to the surface of the support opposite to the surface on which the ink layer is provided. As binder resin used for BC layer, acrylic resin such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymer, ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, Cellulose resins such as cellulose acetate butyrate and nitrocellulose, vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal and polyvinyl pyrrolidone, polyamide resins, polyvinyl toluene resins, coumarone indene resins, polyester resins, polyurethanes Resins, silicone-modified or fluorine-modified urethane and the like can be mentioned.

  These resins may be used in combination. In order to further improve the heat resistance of the BC layer, a resin having a reactive group such as a hydroxyl group may be used among the above resins, and a polyisocyanate or the like may be used in combination as a crosslinking agent to form a crosslinked resin layer. Further, in order to improve the slipperiness with a heating means such as a thermal head, a solid or liquid release agent or lubricant may be added to the BC layer to give heat-resistant slipperiness. Examples of release agents or lubricants include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, oreganopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Agents, fluorine surfactants, organic carboxylic acids and derivatives thereof, fluorine resins, silicone resins, fine particles of inorganic compounds such as talc, silica, molybdenum sulfide, and the like can be used. The preferable addition amount of the lubricant to the BC layer is 5 to 50% by mass, particularly preferably 10 to 30% by mass, based on the total solid content of the BC layer. The thickness of the BC layer is preferably about 0.1 to 10 μm after coating and drying.

(Post-heat treatment area)
In the thermal transfer recording used in the present invention, the transferred surface after dye transfer and the surface of a non-transferable resin layer (hereinafter, also referred to as a non-transfer release layer) face each other, and are not transferable. Post heat treatment is performed by applying heat from the side opposite to the resin layer.

  The non-transferable resin layer used in the present invention can be provided on the same surface as the ink layer in a so-called surface sequential manner. When the non-transferable resin layer is used alone as a sheet, the same support or BC layer as described above can be used.

  The binder resin used for the non-transferable resin layer can be the same as the binder resin used for the ink layer.

  When the non-transferable resin layer is provided in the surface order with the ink layer, the resin layer preferably contains fine particles. This means that when stored in a roll state after coating, the dye migrates slightly to the BC layer, and when the product is in a small volume, the dye migrated to the BC layer is retransferred to the non-transferable resin layer. This is performed for the purpose of preventing the phenomenon of so-called kickback. When kickback occurs, the dye retransferred to the resin layer colors the image receiving surface during printing, and the image quality is significantly impaired. As fine particles, in addition to inorganic fine particles such as silica, alumina and calcium carbonate, fine resin particles such as acrylic resin, fluororesin, polyethylene resin and polystyrene resin, or wax particles can be used. The particle diameter of these fine particles is preferably 0.1 to 50 μm. If the thickness is less than 0.1 μm, the resin layer surface has too little unevenness and has no effect on kickback, and if it exceeds 50 μm, the image surface after printing is roughened and the image quality is impaired. A preferable addition amount of the fine particles is 1 to 50% by mass, particularly preferably 5 to 30% by mass with respect to the total solid content of the resin layer. If the amount is less than 1% by mass, the unevenness of the resin layer surface is so small that the effect on kickback is small, and if it exceeds 50% by mass, the image surface after printing is roughened and the image quality is impaired.

  In the thermal transfer recording method of the present invention, a thermal transfer layer (dye-donating layer) of the thermal transfer recording material and an image receiving material (hereinafter sometimes referred to as an image receiving sheet) are superposed, and then the image information is determined. Heat is applied to the thermal transfer recording material to form an image on the image receiving material with the chelate dye formed by the reaction between the metal ion-containing compound and the dye of the present invention. The metal ion-containing compound may be present in the image receiving material or may be present in a heat-meltable layer provided on the heat-sensitive transfer recording material.

Examples of the metal ion-containing compound include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable. 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 preferred, Ni, Cu, Cr, Co and Zn are more preferred, with Ni being particularly preferred. Specific examples of the metal ion-containing compound include Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and aliphatic salts such as acetic acid and stearic acid, or fragrances such as benzoic acid and salicylic acid. And salts of group carboxylic acids.
Moreover, the complex represented by the following general formula (3) can be particularly preferably used.

General formula (3) [M (Q ₁ ) _l (Q ₂ ) _m (Q ₃ ) _n ] ^{p +} (Y ⁻ ) _P

Wherein M is a metal ion, preferably Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ , Zn ^2+.
Represents. 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) (Nan Edo). 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. These are compounds in which the complex represented by the above general formula is tetradentate or hexadentate. It is determined by the coordination or by the number of Q ₁ , Q ₂ and Q ₃ ligands. 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 (4) is preferable.

In the formula, R ₁₁ and R ₁₃ each represent the same or different alkyl group or aryl group, and R ₁₂ represents an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a hydrogen atom. R ₁₁ , R ₁₂ and R ₁₃ may be substituted with the same substituent as the substituent represented by R ₁ .

  Although the specific example of the said metal ion containing compound is given to the following, this invention is not limited to these.

The addition amount of the metal ion-containing compound used in the present invention is usually preferably 0.5 to 20 g / m ^{2 and} more preferably ¹ to 15 g / m ² with respect to the support.

  The addition amount of the metal ion-containing compound is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass, based on the total solid content of the resin layer. When the amount is less than 0.01% by mass, the effect of addition is small, and when the amount is more than 1% by mass, the above-described kickback is more noticeable.

  In order to improve the releasability between the dye image-receiving layer and the non-heat transferable resin layer in the post-heating region, a release agent may be added or a separate release layer containing a release agent may be provided. As the release agent, reactive curable silicones, phosphate ester surfactants, fluorine compounds, and the like can be used. As for the usage-amount of a mold release agent, 0.5-40 mass% is preferable with respect to solid content of the layer to contain. When providing a release layer, the same binder as that used for the ink layer can be used.

(Protective layer)
The heat transferable protective layer (hereinafter sometimes referred to as a protective transfer layer) used in the present invention is composed of a transparent resin layer serving as a protective layer covering the surface of an image formed by thermal transfer on an image receiving sheet.

  Examples of the resin forming the heat transferable protective layer include polyester resins, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, polycarbonate resins, epoxy-modified resins of these resins, and resins obtained by modifying these resins with silicone. Examples thereof include mixtures of these resins, ionizing radiation curable resins, ultraviolet blocking resins, and the like. Preferred resins include polyester resins, polycarbonate resins, epoxy-modified resins, and ionizing radiation curable resins. The polyester resin is preferably an alicyclic polyester resin in which the diol component and the acid component have one or more alicyclic compounds. As the polycarbonate resin, an aromatic polycarbonate resin is preferable, and an aromatic polycarbonate resin described in JP-A-11-151867 is particularly preferable.

  Examples of the epoxy-modified resin used in the present invention include epoxy-modified urethane, epoxy-modified polyethylene, epoxy-modified polyethylene terephthalate, epoxy-modified polyphenyl sulfite, epoxy-modified cellulose, epoxy-modified polypropylene, epoxy-modified polyvinyl chloride, epoxy-modified polycarbonate, and epoxy. Modified acrylic, epoxy modified polystyrene, epoxy modified polymethyl methacrylate, epoxy modified silicone, copolymer of epoxy modified polystyrene and epoxy modified polymethyl methacrylate, copolymer of epoxy modified acrylic and epoxy modified polystyrene, epoxy modified acrylic and epoxy modified silicone Preferably, epoxy-modified acrylic, epoxy-modified polystyrene, epoxy-modified polymethyl is used. Tacrylate and epoxy-modified silicone, more preferably a copolymer of epoxy-modified polystyrene and epoxy-modified polymethyl methacrylate, a copolymer of epoxy-modified acrylic and epoxy-modified polystyrene, and a copolymer of epoxy-modified acrylic and epoxy-modified silicone. .

<Ionizing radiation curable resin>
An ionizing radiation curable resin can be used as the heat transferable protective layer. By containing it in the thermal transferable protective layer, the plasticizer resistance and scratch resistance are particularly excellent. Known ionizing radiation curable resins can be used without any particular limitation. For example, radically polymerizable polymers or oligomers are crosslinked and cured by ionizing radiation irradiation, and a photopolymerization initiator is added if necessary. And what was polymerized and bridge | crosslinked with the electron beam or the ultraviolet-ray can be used.

(UV blocking resin)
As the heat transferable protective layer, a protective layer containing an ultraviolet blocking resin can be used. The main purpose of the protective layer containing this ultraviolet blocking resin is to impart light resistance to the printed matter. As the ultraviolet blocking resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber with a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, a conventionally known non-reactive organic ultraviolet absorber such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate or hindered amine is added to an addition polymerizable double bond ( Examples thereof include those in which a reactive group such as a vinyl group, an acryloyl group, a methacryloyl group), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group is introduced.

  The main protective layer provided in the heat transferable protective layer having a single layer structure or the heat transferable protective layer having a multilayer structure as described above is usually about 0.5 to 10 μm, although it depends on the kind of the resin for forming the protective layer. Form to thickness.

  The thermal transferable protective layer of the present invention is preferably provided on the support of the thermal transfer sheet via a non-transferable release layer.

  The non-transfer release layer always has an adhesive force between the support and the non-transfer release layer that is greater than the adhesive force between the non-transfer release layer and the thermal transfer protective layer (protective transfer layer). (1) Resin binder for the purpose of increasing the adhesive strength between the non-transferable release layer and the heat transferable protective layer before application of heat to a sufficiently high level relative to that after application of heat. In addition, it contains 30 to 80% by mass of inorganic fine particles having an average particle size of 40 nm or less, or (2) a proportion of 20% by mass or more in total of an alkyl vinyl ether-maleic anhydride copolymer, a derivative thereof, or a mixture thereof. Or (3) containing an ionomer in a proportion of 20% by mass or more. The non-transferable release layer may contain other additives as necessary.

  Examples of the inorganic fine particles include silica fine particles such as anhydrous silica and colloidal silica, and metal oxides such as tin oxide, zinc oxide, and zinc antimonate. The particle diameter of the inorganic fine particles is preferably 40 nm or less. If it exceeds 40 nm, the unevenness on the surface of the heat transferable protective layer is increased due to the unevenness on the surface of the release layer, and as a result, the transparency of the protective layer is lowered, which is not preferable.

  The resin binder to be mixed with the inorganic fine particles is not particularly limited, and any resin that can be mixed can be used. For example, polyvinyl alcohol resins (PVA) of various saponification degrees; polyvinyl acetal resins; polyvinyl butyral resins; acrylic resins; polyamide resins; cellulose resins such as cellulose acetate, alkyl cellulose, carboxymethyl cellulose, hydroxyalkyl cellulose; Examples thereof include resins.

  The blending ratio (inorganic particulate / other blending components) of the inorganic particulates and other blending components mainly composed of a resin binder is preferably in the range of 30/70 or more and 80/20 or less in terms of mass ratio. When the blending ratio is less than 30/70, the effect of the inorganic fine particles becomes insufficient. On the other hand, when the blending ratio exceeds 80/20, the release layer does not become a complete film, and the support and the heat transferable protective layer are in direct contact with each other. End up.

  Examples of the alkyl vinyl ether-maleic anhydride copolymer or derivative thereof described in (2) above include those in which the alkyl group of the alkyl vinyl ether moiety is a methyl group or an ethyl group, and the maleic anhydride moiety is partially or completely In addition, a half ester with alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc.) can be used.

  The release layer may be formed only with an alkyl vinyl ether-maleic anhydride copolymer, a derivative thereof, or a mixture thereof, but for the purpose of adjusting the peeling force between the release layer and the protective layer, A resin or fine particles may be further added. In that case, it is desirable that the release layer contains 20% by mass or more of an alkyl vinyl ether-maleic anhydride copolymer, a derivative thereof, or a mixture thereof. When the content is less than 20% by mass, the effect of the alkyl vinyl ether-maleic anhydride copolymer or its derivative cannot be sufficiently obtained.

  The resin or fine particles blended in the alkyl vinyl ether-maleic anhydride copolymer or derivative thereof is not particularly limited as long as it can be mixed and can provide high film transparency at the time of film formation, and any material can be used. I can do it. For example, the above-mentioned inorganic fine particles and resin binders that can be mixed with the inorganic fine particles are preferably used.

  As the ionomer described in (3), for example, Surlyn A (manufactured by DuPont), Chemipearl S series (manufactured by Mitsui Petrochemical Co., Ltd.), or the like can be used. Further, for example, the above-mentioned inorganic fine particles, a resin binder that can be mixed with the inorganic fine particles, or other resins and fine particles can be further added to the ionomer.

  In order to form a non-transferable release layer, a coating solution containing any one of the above components (1) to (3) in a predetermined blending ratio is prepared, and this coating solution is applied to a gravure coating method or a gravure reverse coating. The coated layer is dried on a support by a known technique such as a method. The thickness of the non-transferable release layer is usually about 0.1 to 2 μm after drying.

  The heat transferable protective layer (protective transfer layer) laminated on the support with or without a non-transferable release layer may have a multilayer structure or a single layer structure. Good. In the case of a multi-layer structure, in addition to the main protective layer, which is the main component for imparting various durability to the image, thermal transfer protection is provided to enhance the adhesion between the heat transfer protective layer and the image receiving surface of the print. An adhesive layer disposed on the outermost surface of the layer, an auxiliary protective layer, and a layer for adding a function other than the original function of the protective layer (for example, an anti-counterfeit layer, a hologram layer, etc.) may be provided. The order of the main protective layer and the other layers is arbitrary, but in general, it is between the adhesive layer and the main protective layer so that the main protective layer becomes the outermost surface of the image receiving material or the image receiving surface of the image receiving sheet after transfer. Place other layers.

  An adhesive layer (hereinafter sometimes referred to as a heat-sensitive adhesive layer) may be formed on the outermost surface of the heat transferable protective layer. The adhesive layer may be formed of a resin having good adhesiveness when heated, such as acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, and polyamide resin. it can. In addition to the above resin, the above-mentioned ionizing radiation curable resin, ultraviolet blocking resin and the like may be mixed as necessary. The thickness of the adhesive layer is usually 0.1 to 5 μm.

  In order to form a thermal transferable protective layer on a non-transferable release layer or on a support, for example, a protective layer coating solution containing a protective layer forming resin, or an adhesive layer coating solution containing a thermal adhesive resin In addition, a coating solution for forming a layer to be added if necessary is prepared in advance, and these are applied in a predetermined order on a non-transferable release layer or a support and dried. Each coating solution may be applied by a conventionally known method. Moreover, you may provide an appropriate primer layer between each layer.

<UV absorber>
The heat transferable protective layer (when the heat transferable protective layer comprises a plurality of layers, at least one layer thereof) preferably contains an ultraviolet absorber, but when it is contained in the transparent resin layer, after the transfer of the protective layer Since the transparent resin layer is present on the outermost surface of the printed material, the effect is reduced over time due to the influence of the environment and the like over a long period of time. Therefore, the transparent resin layer is particularly preferably contained in the heat-sensitive adhesive layer.

  Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers. Specific examples thereof include Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 328 , Tinuvin 312, Tinuvin 315 (manufactured by Ciba Geigy), Sumisorb-110, Sumisorb-130, Sumisorb-140, Sumisorb-200, Sumisorb-250, Sumisorb-300, Sumisorb-320, Sumisorb-340, Sumisorb-340, Sumisorb-340, 400 (manufactured by Sumitomo Chemical Co., Ltd.), Mark LA-32, Mark LA-36, ark 1413 can be obtained from the market (Adeka Argus Chemical Co., Ltd.) trade names of, any can be used in the present invention.

  Further, a random copolymer having a Tg of 60 ° C. or higher, preferably 80 ° C. or higher, in which a reactive ultraviolet absorber and an acrylic monomer are randomly copolymerized may be used.

  The above-mentioned reactive ultraviolet absorbers are conventionally known salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, nickel chelate-based, hindered amine-based non-reactive ultraviolet absorbers such as vinyl group and acryloyl group, Addition-polymerizable double bonds such as methacryloyl groups, or those having introduced an alcoholic hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group or the like can be used. Specifically, UVA635L, UVA633L (manufactured by BASF Japan), PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like can be obtained from the market, and any of them can be used in the present invention.

  The amount of the reactive ultraviolet absorbent in the random copolymer of the reactive ultraviolet absorbent and the acrylic monomer as described above is in the range of 10 to 90 mass%, preferably 30 to 70 mass%. Moreover, the molecular weight of such a random copolymer can be about 5000-250,000, Preferably it can be about 9000-30000. The above-mentioned ultraviolet absorber and the random copolymer of the reactive ultraviolet absorber and the acrylic monomer may be contained alone or in combination. The addition amount of the random copolymer of the reactive ultraviolet absorber and the acrylic monomer is preferably 5 to 50% by mass with respect to the layer to be contained.

  Of course, other light-proofing agents may be included in addition to the ultraviolet absorber. Here, the light-proofing agent is an agent that prevents or alters the degradation or decomposition of the dye by absorbing or blocking the action of altering or decomposing the dye, such as light energy, thermal energy, and oxidizing action. Besides antioxidants, antioxidants and light stabilizers conventionally known as additives for synthetic resins and the like can be mentioned. Also in that case, it may be contained in at least one of the heat transferable protective layers, that is, at least one of the release layer, the transparent resin layer, and the heat-sensitive adhesive layer, but is particularly preferably contained in the heat-sensitive adhesive layer.

  Examples of the antioxidant include primary antioxidants such as phenols, monophenols, bisphenols, and amines, and secondary antioxidants such as sulfur and phosphorus. Examples of light stabilizers include hindered amines.

  Although the usage-amount of said light-proofing agent containing an ultraviolet absorber is not specifically limited, Preferably it is 0.05-10 mass parts per 100 mass parts of resin which forms the layer to contain, Preferably it is 3-10 mass parts Use as a percentage. If the amount used is too small, it is difficult to obtain an effect as a light-proofing agent, while if too large, it is uneconomical.

In addition to the above light-proofing agent, various additives such as a fluorescent brightening agent and a filler can be simultaneously added to the adhesive layer in an appropriate amount.
The thermal transferable protective layer may be provided in the surface order with the ink layer of the thermal transfer sheet as described above, or may be provided alone on a separate support to form a protective layer transfer sheet.

(Base material of image receiving sheet)
The substrate of the image receiving sheet (hereinafter also referred to as a support) has a role of holding the dye image receiving layer, and heat is applied at the time of thermal transfer, so that it does not interfere with handling even in an overheated state. It is preferable to have strength.

  There are no particular limitations on the material of such a base material. For example, condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality 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, polyetheretherketone, polysulfone, polyethylene Examples include ether sulfone, 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 a filler to these synthetic resins and a foamed foam sheet can also be used, and are not particularly limited.

  Moreover, the laminated body by the arbitrary combinations of the said base material can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper, or synthetic paper of cellulose synthetic paper and a plastic film. The thickness of these supports may be arbitrary and is usually about 10 to 300 μm.

  In order to obtain higher printing sensitivity and high image quality without density unevenness or white spots, it is preferable to have a layer having fine voids. As a layer having fine voids (hereinafter sometimes referred to as a fine void resin layer), a plastic film or synthetic paper having fine voids inside can be used. In addition, a layer having fine voids can be formed on various supports by various coating methods. As a plastic film or synthetic paper having fine voids, polyolefin, especially polypropylene, is mainly blended with an inorganic pigment and / or a polymer incompatible with polypropylene, and these are used as void (void) formation initiators. A plastic film or synthetic paper obtained by stretching and forming a mixture of the above is preferable. If these are mainly polyester, etc., the viscoelastic or thermal properties make the cushioning and heat insulation properties inferior to those mainly made of polypropylene. Unevenness is also likely to occur.

Considering these points, the elastic modulus at 20 ° C. of the plastic film and the synthetic paper is preferably 5 × 10 ⁸ Pa to 1 × 10 ¹⁰ Pa. In addition, since these plastic films and synthetic paper are usually formed by biaxial stretching, they shrink by heating. When these are left at 110 ° C. for 60 seconds, the shrinkage is 0.5 to 2.5%. The plastic film and the synthetic paper described above may be combined with each other as a single layer including fine voids, or may have a plurality of layers. In the case of a plurality of layer structures, all the layers constituting the structure may contain fine voids, or a layer containing no fine voids may be contained. A white pigment may be mixed in the plastic film or synthetic paper as a concealing agent as necessary. In order to increase whiteness, an additive such as a fluorescent brightener may be included. The layer having fine voids preferably has a thickness of 30 to 80 μm.

  As a layer having fine voids, a layer having fine voids can be formed on a substrate by a coating method. As the plastic resin to be used, known resins such as polyester, urethane resin, polycarbonate, acrylic resin, polyvinyl chloride, and polyvinyl acetate can be used singly or in combination.

If necessary, on the surface of the substrate opposite to the side where the dye image-receiving layer is provided, for the purpose of preventing curling, polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, polycarbonate, etc. A layer of resin or synthetic paper can be provided. As a bonding method, for example, known lamination methods such as dry lamination, non-solvent (hot melt) lamination, EC lamination method and the like can be used, but preferred methods are dry lamination and non-solvent lamination. Examples of the adhesive suitable for the non-solvent lamination method include Takenate 720L manufactured by Takeda Pharmaceutical Company Limited, and examples of the adhesive suitable for dry lamination include Takelac A969 / Takenate A manufactured by Takeda Pharmaceutical Company Limited. -5 (3/1), manufactured by Showa Polymer Co., Ltd., Polysol PSA SE-1400, Vinylol PSA AV-6200 series and the like. The amount of these adhesives, from about 1-8 g / ^{m 2} on a solids, and preferably from 2 to 6 g / ^{m 2.}

  When the plastic film and the synthetic paper as described above, or between them, or various papers and the plastic film or the synthetic paper are laminated, they can be bonded together by an adhesive layer.

  For the purpose of increasing the adhesive strength between the substrate and the dye image-receiving layer (sometimes referred to as a thermal transfer image-receiving layer), it is preferable to subject the surface of the substrate to various primer treatments and corona discharge treatments.

(Image receiving sheet intermediate layer)
At least one or more intermediate layers may be provided between the dye image-receiving layer and the image-receiving sheet substrate. The intermediate layer means all layers provided between the image receiving layer and the substrate, such as an adhesive layer (primer layer), a barrier layer, an ultraviolet absorbing layer, a foamed layer, an antistatic layer, etc. Either can be used. Furthermore, it is preferable to add a white pigment such as titanium oxide to the intermediate layer in order to conceal the glare and unevenness of the substrate, since the degree of freedom in selecting the substrate is increased. The content of the intermediate layer resin and the white pigment is preferably 30 to 300 parts by mass of the white pigment solid content with respect to 100 parts by mass of the resin solid content. Is more preferable.

  As the intermediate layer, a layer obtained by curing a thermoplastic resin, a thermosetting resin, or a thermoplastic resin having a functional group by using various additives or other methods can be used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, polyester, chlorinated polypropylene, modified polyolefin, urethane resin, acrylic resin, polycarbonate, ionomer, resin having a monofunctional and / or polyfunctional hydroxyl group-containing prepolymer cured with isocyanate or the like Etc. can be used.

(Image receiving layer)
The dye image-receiving layer is composed of a binder resin and, if necessary, various additives such as a release agent and a metal ion-containing compound on one surface of the substrate. When the metal ion-containing compound is added, the addition amount is usually preferably 10 to 60% by mass and more preferably 20 to 50% by mass with respect to the solid content of the image receiving layer.

  A well-known thing can be used for binder resin, It is preferable to use what a pigment | dye tends to dye | stain. Specifically, polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene Resins, polyamide resins, phenoxy resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, polyurethane, polycarbonate, acrylic resins, ionomers, cellulose derivatives, etc. can be used alone or as a mixture, Among these, polyester resins and vinyl resins are preferable.

  It is preferable to add a release agent to the dye image-receiving layer in order to prevent thermal fusion with the ink layer. As the mold release agent, a phosphoric ester plasticizer, a fluorine compound, silicone oil (including reaction curable silicone) and the like can be used, and among these, silicone oil is preferable. As the silicone oil, various modified silicones such as dimethyl silicone can be used. Specifically, amino-modified silicones, epoxy-modified silicones, alcohol-modified silicones, vinyl-modified silicones, urethane-modified silicones, and the like can be blended or polymerized using various reactions. One or more release agents are used. Further, the addition amount of the release agent is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the image receiving layer forming resin. When the range of the addition amount is not satisfied, problems such as fusion between the thermal transfer sheet and the image receiving layer of the image receiving sheet or a decrease in printing sensitivity may occur. These releasing agents may not be added to the image receiving layer, but may be provided separately as a releasing layer on the image receiving layer.

(Layer structure, coating method, etc.)
The above dye image-receiving layer is a reverse coating using a bar coater, a gravure printing method, a screen printing method, a roll coating method, a gravure plate, on a substrate, dissolved or dispersed in a solvent such as water or an organic solvent. It can be formed by applying by ordinary methods such as a roll coating method, an air knife coating method, a spray coating method, a curtain coating method, and an extrusion coating method, and then drying. The barrier layer, the intermediate layer, and the back layer are formed by the same method as that for the image receiving layer. In addition, the image receiving layer is not only formed by applying the coating solution directly on the substrate and drying as described above, but also having an image receiving layer formed in advance on another support, The image receiving layer may be transferred and formed. Further, two or more layers can be coated by the simultaneous coating method, and in particular, all the layers can be coated by one coating.
The thickness of the image receiving layer is the thickness after coating and drying, and is preferably about 0.1 to 10 μm.

(Image receiving sheet shape)
The image receiving sheet used in the present invention may be supplied to the printer as a single sheet or as a roll. The sheet supply refers to, for example, a form in which an image receiving sheet is cut into a certain size, about 50 sheets are put in a cassette and mounted on a printer. The roll form is a form in which the image-receiving sheet is supplied to the printer in that form and cut into a desired size after printing. In particular, the latter is preferable because troubles in the conveyance system such as feeding failure and ejection failure such as inserting two sheets can be solved and the capacity of the printable sheet can be increased.

  When supplying the image receiving sheet in a roll form, particularly when the postcard specification is as described above, or when using a label or a seal type image receiving sheet, a design mark such as a postal code frame formed on the back side, In order to align the cutting position with the half-cut position of the seal, a detection mark can be provided on the back side.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
<Preparation of ink>
The following raw materials were mixed to obtain a uniform solution ink containing the pigment according to the present invention. The solubility of the coloring matter of the present invention was good, and ink suitability was also good.

0.68 g of the dye of the present invention (Exemplary dye 1)
Polyvinyl acetoacetal resin (KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.08 g
Methyl ethyl ketone 26.4ml
Toluene 1.6ml

<Production of thermal transfer recording material>
The ink is applied and dried on a polyethylene terephthalate base with a thickness of 4.5 μm using a wire bar so that the coating amount after drying is 2.3 g / m ² to form a heat-sensitive transfer layer on the polyethylene phthalate film. A heat-sensitive transfer recording material 1 was prepared.

In addition, the back surface of the said polyethylene terephthalate base is provided with the nitrocellulose layer containing silicon modified urethane resin (SP-2105, Dainichi Seika Co., Ltd.) as a sticking prevention layer.
In the same manner as described above, thermal transfer recording materials 2 to 6 (reference invention) using the dyes shown in Table 1 were prepared.

<Production of image receiving material>
The coating amount after drying an image-receiving layer coating liquid having the following composition on a support laminated with polyethylene on both sides of paper (including white pigment (TiO ₂ ) and bluing agent on one polyethylene layer) is 7.2 g. Thus, the image receiving material 1 was prepared by coating and drying.

<Preparation of image-receiving layer coating solution>
Metal ion-containing compound (Exemplary M-31) 4.0 g
Polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical Co., Ltd.) 6.0 g
Polyester modified silicon 0.3g

<Thermal transfer recording method>
Each of the thermal transfer recording materials 1 to 6 and the image receiving material 1 were overlapped, a thermal head was applied from the back side of the thermal transfer recording material, and image recording was performed with a thermal printer to obtain image samples 1 to 6.
The maximum density of the obtained image samples 1 to 6 and the sensitivity of the thermal transfer recording material were evaluated as follows.

《Maximum concentration》
The maximum reflection density (usually the portion where the application time was the maximum) of the image sample was measured with a densitometer X-rite 310TR (manufactured by X-rite).

<< Evaluation of sensitivity >>
The relative applied energy of each material when the applied energy when the density of the image formed with the thermal transfer recording material 5 is 1.0 was determined. The smaller the number, the higher the sensitivity.
The results are shown in Table 1.

As Table 1 shows, a high-density and high-sensitivity image can be obtained by using the thermal transfer recording material using the dye of the present invention (Exemplary dye 1) .

Example 2
In the preparation of the image receiving material 1 of Example 1, an image receiving material 2 having the same composition as that of the image receiving material 1 except that the metal ion-containing compound M-31 was further removed from the image receiving material 1 was prepared. And each of the image samples 1 to 6 of Example 1 were overlapped and applied with a weight of 20 kg / m ² at 40 ° C. and left for 48 hours, and then peeled off to visually observe the degree of transfer of the dye to the image receiving material 2. Observed at.

  As a result, no dye transfer to the image receiving material 2 was observed in any of the images recorded by the thermal transfer recording method of the present invention, but dye transfer was observed in the image sample 4. That is, it can be seen that according to the thermal transfer recording method of the present invention, an image having excellent fixability can be obtained.

Example 3
<Production of thermal transfer sheet>
[Preparation of thermal transfer sheet 1]
(Preparation of support A with back coat layer)
A backcoat layer coating solution 1 having the following composition is applied to one side of a 4.5 um thick polyethylene terephthalate film with an easy-contact layer (Lumirror manufactured by Toray Industries, Inc.) using a gravure coating method, dried, and then heated and cured. The support A having a back coat layer with a dry film thickness of 1.0 μm was prepared.

<Preparation of backcoat layer coating solution 1>
Polyvinyl butyral resin (Sekisui Chemical Co., Ltd. ESREC BX1) 3.5 parts by mass Phosphate-based surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Prisurf A208S)
3.0 parts by mass phosphate ester surfactant (Phosphanol RD720 manufactured by Toho Chemical Co., Ltd.)
0.3 part by mass polyisocyanate (Dainippon Ink & Chemicals, Barnock D75045)
19.0 parts by mass Talc (manufactured by Nippon Talc Co., Ltd. Y / X = 0.03) 0.2 parts by mass Methyl ethyl ketone 35.0 parts by mass Toluene 35.0 parts by mass

[Formation of dye layer (ink layer) and protective transfer layer]
Each dye layer formed using a yellow dye coating liquid 1, a magenta dye coating liquid 1, and a cyan dye coating liquid 1 having the following composition on the surface opposite to the back coat surface of the support A with the back coat layer ( A dry transfer film thickness of 1 μm) and a multilayer constitution protective transfer layer (a three-layer constitution of a non-transferable release layer / protective transfer layer / adhesive layer) were provided in the surface order by a gravure method to produce a thermal transfer sheet 1. .

[Each dye layer]
<Yellow dye coating solution 1>
Yellow dye (Exemplary dye 1) 4.5 parts by mass polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS5) 5.0 parts by mass urethane-modified silicone resin (Dairoma Seika Co., Ltd., Dialomer SP2105)
0.5 parts by mass Methyl ethyl ketone 45.0 parts by mass Toluene 45.0 parts by mass

<Magenta dye coating solution 1>
Magenta dye (MA) 4.0 parts by mass polyvinylacetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS5) 5.5 parts by mass urethane-modified silicone resin (manufactured by Dainichi Seika Co., Ltd., Dialomer SP2105)
0.5 parts by mass Methyl ethyl ketone 45.0 parts by mass Toluene 45.0 parts by mass

<Cyan dye coating solution>
Cyan dye (CY) 4.0 parts by mass polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS5)
5.5 parts by mass urethane-modified silicone resin (Dairoma SP2105, manufactured by Dainichi Seika Co., Ltd.)
0.5 parts by mass Methyl ethyl ketone 45.0 parts by mass Toluene 45.0 parts by mass

[Multi-layer protective transfer layer]
(Non-transferable release layer)
A non-transferable release layer coating liquid 1 having the following composition was applied by a gravure coating method so that the solid content after drying was 0.5 g / m ² and dried to form a non-transferable release layer. .

<Non-transferable release layer coating solution 1>
Colloidal silica (Snowtex 50, manufactured by Nissan Chemical Co., Ltd.) 1.5 parts by mass polyvinyl alcohol 4.0 parts by mass ion-exchanged water 3.0 parts by mass denatured ethanol 10 parts by mass

(Protective transfer layer)
On the formed non-transferable release layer, a protective transfer layer coating solution 1 having the following composition was applied and dried by a gravure coating method so that the solid content after drying was 2.0 g / m ² . A protective transfer layer was formed.

<Protective transfer layer coating solution 1>
Acrylic resin 15 parts by mass Vinyl chloride-vinyl acetate copolymer 5 parts by mass Copolymerized resin reactive UV absorber (UVA-635L manufactured by BASF Japan) 40 parts by mass polyethylene wax 0.3 parts by mass polyester resin 0 .1 part by mass Methyl ethyl ketone 40 parts by mass Toluene 40 parts by mass Zinc antimonate (Sellnax manufactured by Nissan Chemical Co., Ltd.) 20 parts by mass

(Adhesive layer)
On the protective transfer layer formed above, the adhesive layer coating solution 1 having the following composition was applied and dried by a gravure coating method so that the solid content after drying was 2.0 g / m ^2. Formed.

<Adhesive layer coating solution 1>
Vinyl chloride-vinyl acetate copolymer 20 parts by mass Methyl ethyl ketone 100 parts by mass Toluene 100 parts by mass

  As described above, a multi-layered protective transfer layer provided with a protective transfer layer, which is a laminate of the protective transfer layer and the adhesive layer, on the non-transferable release layer was prepared.

<< Preparation of thermal transfer image-receiving sheet >>
[Preparation of thermal transfer image-receiving sheet 1]
A thermal transfer image receiving sheet 1 was produced according to the following contents.

(Production of support)
As a support for the image-receiving sheet, coated paper (US basis weight 157 g / m ² OK Top Coat S, manufactured by Oji Paper Co., Ltd.) was used, and after one side was subjected to corona discharge treatment, High density polyethylene (J-Rex LZ01392, density 0.952, manufactured by Nippon Polyolefin Co., Ltd., hereinafter abbreviated as HDPE) blended with 15% by mass of an ethylene α-olefin copolymer (Tuffmer A4085, Mitsui Petrochemical Co., Ltd.), Two layers of polypropylene (J-Alomer LR7115, density 0.905, manufactured by Nippon Polyolefin Co., Ltd., hereinafter abbreviated as PP) are coextruded so that the HDPE side is in contact with the coated paper by a coextrusion coating method using a known multilayer T die. And laminated. Further, after the corona discharge treatment is performed on the PP surface which is on the outside, the back layer coating solution 1 having the following composition is applied and dried so that the dry solid content is 1.5 g / m ² . Support B was prepared. The back surface resin layer was processed so that the HDPE layer of the ethylene α-olefin copolymer blend was 14 μm and the PP layer was 19 μm, for a total of 33 μm.

<Preparation of backside layer coating solution 1>
Acrylic resin (BR85 manufactured by Mitsubishi Rayon Co., Ltd.) 19.8 parts by weight Nylon filler (MW330 manufactured by Shinto Paint Co., Ltd.) 0.6 parts by weight Methyl ethyl ketone 39.8 parts by weight Toluene 39.8 parts by weight

(Preparation of thermal transfer image receiving sheet)
On the other hand, a foamed polypropylene sheet having a thickness of 35 μm (manufactured by 35MW846 Mobile Plastics Europe) was used as a resin layer having fine voids, and an intermediate layer coating solution and a dye image-receiving layer coating having the following composition were formed on one surface thereof. The foam is coated with the liquid by the gravure reverse coating method so that the coating thickness when dried is 1 μm and 3 μm, respectively, and dried to produce a foamed polypropylene sheet in which the intermediate layer and the dye image-receiving layer are laminated. did.

  Next, the side of the foamed polypropylene sheet on which the intermediate layer and the dye image-receiving layer are not provided (foamed polypropylene sheet surface) and the side of the support B on which the back resin layer is not provided (coated paper surface) A thermal transfer image-receiving sheet 1 was prepared by laminating with an adhesive having the following composition by a dry laminating method.

<Preparation of intermediate layer coating solution>
Urethane resin (Nipporan 5199, manufactured by Nippon Polyurethane Co., Ltd.) 5.7 parts by mass Titanium oxide (TCA888, manufactured by Tochem Products) 11.4 parts by mass Optical brightener (Ubitex OB, manufactured by Ciba Geigy Japan) 0.2 Isocyanate (Takenate A14, Takeda Pharmaceutical Company Limited) 2.0 parts by mass Methyl ethyl ketone 15.5 parts by mass Toluene 15.5 parts by mass Isopropyl alcohol 7.7 parts by mass

<Preparation of dye image-receiving layer coating solution>
Vinyl chloride-vinyl acetate copolymer (Denka Vinyl # 1000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) 7.2 parts by mass Vinyl chloride-styrene-acrylic copolymer (Denka Rack # 400, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.6 parts by mass polyester ( Byron 600 manufactured by Toyobo Co., Ltd. 11.2 parts by mass of metal ion-containing compound (Exemplary M-31) 8.0 parts by mass vinyl-modified silicone (X621212 manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 parts by mass Catalyst: CAT PLR5 (Shin-Etsu Chemical) 1.0 mass part catalyst: CAT PL50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.2 mass parts Solvent: methyl ethyl ketone 39.0 mass parts Solvent: toluene 39.0 mass parts

<Preparation of print sample>
Using the thermal transfer sheet 1 and the thermal transfer image receiving sheet 1 produced as described above, a sublimation thermal transfer printer (RC-602 type manufactured by Konica Minolta Photo Imaging Co., Ltd.) is used, and yellow, Each step pattern of magenta, cyan, and neutral (yellow, magenta, and cyan three-color overlap) was transferred, and then a transparent protective layer was transferred onto the image to prepare a print sample.

  When the obtained image sample was evaluated in the same manner as in Example 1, it was possible to obtain an image having high density, high sensitivity, and excellent fixability.

Example 4
In place of the metal ion-containing compound example M-31 in Examples 1 and 3, only the use of other example compounds was used, and the effects of the present invention were confirmed.

As described above, the dye according to the present invention (Exemplary dye 1) can be applied to a thermal transfer recording material for full-color image recording, and the thermal transfer recording material according to the present invention has a high density, high sensitivity, and excellent fixability. It can be seen that this is a thermal transfer recording material.

Claims (3)

A thermal transfer recording material comprising a dye represented by the following general formula (2) .

[Wherein, R ₉ and R ₁₀ represent a methyl group . ] The heat-sensitive transfer recording material having a dye-donor layer containing the color-containing represented by the general formula on a support (2), overlapping the image-receiving material is heated in accordance with sensitive transfer recording material to the image information, wherein A thermal transfer recording method comprising forming an image on an image receiving material. The heat-sensitive transfer recording material having a dye-donor layer containing the color-containing represented by the general formula on a support (2), overlapping the image receiving material having a dye image-receiving layer containing a metal ion-containing compound on a support, A thermal transfer recording method, wherein the thermal transfer recording material is heated according to image information, and a metal chelate dye image is formed on the image receiving material by a reaction between the dye and the metal ion-containing compound.