JP4680085B2 - Thermal transfer recording material, thermal transfer recording method and thermal transfer recording dye - Google Patents

Description

The present invention relates to a thermal transfer recording material and the thermal transfer recording how.

  Conventionally, a color image recording technique using a thermal transfer material has been studied as a method for obtaining a color hard copy.

  The thermal transfer material has advantages such as easy operation and maintenance, downsizing and cost reduction of the apparatus, and low running cost.

  By the way, in thermal transfer recording with thermal transfer, the dye is transferred by thermal energy, so when trying to increase the sensitivity (shortening the transfer time), the dye is thermally made highly diffusive so that the sensitivity is high. Is achieved. Therefore, in the thermal transfer recording of the thermal transfer system, the dye used for the thermal transfer material is important, but conventionally, the sensitivity and the maximum density are inferior (for example, see Patent Document 1) or the maximum density is good. There was a problem that the stability of the obtained image, in particular, fixing property and light resistance were inferior (see, for example, Patent Document 2).

  On the other hand, thermal transfer 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 (see, for example, Patent Documents 3 to 5). . The image formed using the chelate dye after disclosed in the patent is excellent in light resistance and fixability, but is not fully satisfactory in terms of the sensitivity of the thermal transfer material and the storage stability of the material itself, Further improvements were desired.

  The post-chelate dyes disclosed in the above patents form bidentate or tridentate chelate dyes, and the azo group of the chromophore is used as a group that coordinates with metal ions. . In thermal transfer recording using these dyes, the hue difference between the chelate dye and the chelate dye is large, so if the chelate reaction during image formation is insufficient, the unreacted post-chelate dye is absorbed. Further improvement in color reproduction is desired when a residual color remains or when a full color image is obtained due to irregular absorption of the formed chelate dye itself.

On the other hand, an example using a dye that does not use an azo group has been disclosed in order to solve the above problems, but improvement is seen in terms of color reproduction (for example, see Patent Documents 6 to 8). The density, sensitivity, and hue are insufficient, and further improvement has been desired.
Japanese Patent Laid-Open No. 10-864 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 JP-A-9-131973 JP-A-11-78258

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel thermal transfer recording material, thermal transfer recording method, and method for obtaining an image having high density, high sensitivity, and good fixability. It is to provide a dye for thermal transfer recording.

〔式中、Ｍ ^２+ はニッケルイオンを表し、Ｒ _２１ 及びＲ _２２ はアルキル基、シクロアルキ
ル基、アリール基または複素環基を表し、Ｒ _２３ は水素原子または置換基を表す。Ｒ _２３ が置換基を表すとき、Ｒ _２１ もしくはＲ _２２ と互いに結合して環を形成してもよい。〕
（２）支持体上に上記色素１−４、１−２２、１−４４、１−５３、１−７７及び１−７９の少なくとも１種を含有する色素供与層を有する感熱転写記録材料に、支持体上に上記一般式（３）で表される金属イオン含有化合物を含有する色素受像層を有する受像材料を重ね、該感熱転写記録材料を画像情報に応じて加熱し、該色素を色素受像層に転写させた後、該色素と該金属イオン含有化合物との反応により該受像材料中に高濃度、高感度及び耐光性を備えた金属キレート色素画像を形成することを特徴とする感熱転写記録方法。
本発明の参考発明として下記１〜６が挙げられる。

The object of the present invention has been achieved by the following constitutions (1) to (2) .
(1) a thermal transfer recording material having a dye-donating layer containing at least one of the following dyes 1-4, 1-22, 1-44, 1-53, 1-77 and 1-79 on a support; An image receiving material having a dye image-receiving layer containing a metal ion-containing compound represented by the following general formula (3) on a support, and forming a metal chelate dye image having high density, high sensitivity and light resistance A heat-sensitive transfer recording material, characterized in that:

[ Wherein M ²⁺ represents a nickel ion, R ₂₁ and R ₂₂ represent an alkyl group, a cycloalkyl,
Represents a hydrogen group, an aryl group or a heterocyclic group, and R ₂₃ represents a hydrogen atom or a substituent. When R ₂₃ represents a substituent, it may be bonded to R ₂₁ or R ₂₂ to form a ring. ]
(2) a thermal transfer recording material having a dye-donating layer containing at least one of the dyes 1-4, 1-22, 1-44, 1-53, 1-77 and 1-79 on a support; An image-receiving material having a dye image-receiving layer containing the metal ion-containing compound represented by the above general formula (3) is superimposed on a support, the heat-sensitive transfer recording material is heated according to image information, and the dye is dye-received. A thermal transfer recording comprising forming a metal chelate dye image having a high density, high sensitivity and light resistance in the image receiving material by transferring the dye to the metal ion-containing compound after being transferred to a layer Method.
The following 1-6 are mentioned as reference invention of this invention.

  1. A thermal transfer recording material comprising at least one dye represented by the following general formula (1).

(In the formula, R ₁ represents a primary alkyl group having 4 or less carbon atoms, a secondary alkyl group, a secondary cycloalkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group, and R ₂ represents R ₃ represents a hydrogen atom, an alkyl group or a cycloalkyl group, X represents —N═ or —C (R ₄ ) ═, R ₄ represents a hydrogen atom or a substituent, Z ₁ represents a group of nonmetallic atoms necessary to form a 5- to 6-membered nitrogen-containing heterocyclic ring together with —N—C—N— part, and Z ₂ represents 5 to 6 together with —N—C═N— part. Represents a group of non-metallic atoms necessary to form a membered nitrogen-containing heterocycle, and these heterocycles may have a substituent.
2. 2. The thermal transfer recording material as described in 1 above, wherein the dye represented by the general formula (1) is represented by the following general formula (2).

(Wherein, R _1, R ₂ and R ₃ have the same meanings as R _1, R ₂ and R ₃ in formula (1) .R ₅ represents a hydrogen atom or a substituent.)
3. A thermal transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) described in 1 or the general formula (2) described in 2 above is provided on the support. And an image receiving material having a dye image receiving layer, and the thermal transfer recording material is heated according to image information to transfer the dye to the dye image receiving layer, and then an image is formed on the image receiving material. Thermal transfer recording method.

  4). A thermal transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) described in 1 or the general formula (2) described in 2 above on a support, and a support An image receiving material having a dye image-receiving layer containing a metal ion-containing compound is superimposed thereon, and the thermal transfer recording material is heated according to image information to transfer the dye to the dye image-receiving layer, and then the dye and the metal A thermal transfer recording method, wherein a metal chelate dye image is formed in the image receiving material by a reaction with an ion-containing compound.

  5. 5. The thermal transfer recording method as described in 4 above, wherein the metal ion-containing compound is represented by the following general formula (3).

(Wherein M ²⁺ represents a divalent metal ion, R ₂₁ and R ₂₂ represent an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂₃ represents a hydrogen atom or a substituent. _{When 23} represents a substituent, it may be bonded to R ₂₁ or R ₂₂ to form a ring.)
6). A thermal transfer recording dye represented by the general formula (1) described in 1 or the general formula (2) described in 2 above.

The present invention, high density, high sensitivity, and excellent image fixability can be provided a novel heat-sensitive transfer recording material and thermal transfer recording how to obtain.

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

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 primary alkyl group having 4 or less carbon atoms, a secondary alkyl group, a secondary cycloalkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group. Examples of the _primary alkyl group having 4 or less carbon atoms represented by R ₁ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an isobutyl group. Examples of secondary alkyl groups include isopropyl and sec-butyl groups. Examples of the secondary cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridyl group, a pyrazinyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, and a pyrazolyl group. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl and the like. Examples of the carbamoyl group include an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a butylaminocarbonyl group, a cyclohexylaminocarbonyl group, a phenylaminocarbonyl group, and a 2-pyridylaminocarbonyl group. In the general formula (1), R ₁ is preferably a primary alkyl group or a secondary alkyl group having 4 or less carbon atoms, preferably a methyl group or an isopropyl group, and particularly preferably a methyl group.

In the general formula (1), R ₂ represents a hydrogen atom or a substituent. Although the substituent represented by R ₂ is not particularly limited, for example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group) , Trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, adamantyl 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 vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl group) -3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4 Hexenyl group, cyclohexenyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkynyl group (eg, propargyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group) Group, imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.) Arylsulfinyl group (eg, phenylsulfinyl group), phosphono group, acyl group (eg, acetyl group, pivaloyl group, benzoyl group), carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group) Butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylamino) Sulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide) Group), cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyl group) Si group etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg acetyloxy group, benzoyloxy group etc.), sulfonic acid group, salt of sulfonic acid, aminocarbonyloxy group, amino group (eg amino group, Ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group) 2-pyridylamino group, etc.), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2- Pyridylaminoureido Etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl) Groups), heterocyclic thio groups, 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.

In the general formula (1), R ₁ is preferably an alkyl group or an aryl group, more preferably an alkyl group, and particularly preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. In the general formula (1), R ₂ is preferably a hydrogen atom.

In the general formula (1), R ₃ represents a hydrogen atom, an alkyl group or a cycloalkyl group. Examples of the alkyl group represented by R ₃ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, neopentyl, and 1-ethyl. A pentyl group, n-octyl group, n-nonyl group, n-undecyl group, etc. can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. In the general formula (1), R ₃ is preferably a hydrogen atom or an alkyl group.

In the general formula (1), X represents —N═ or —C (R ₄ ) ═, and R ₄ represents a hydrogen atom or a substituent. When R ₄ represents a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent represented by R ₂ . These substituents may be further substituted with the same substituent. In the general formula (1), X preferably represents -N =.

In the general formula (1), Z ₁ represents a group of nonmetallic atoms necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring together with the —N—C—N— moiety, and Z ₂ represents —N—C═ This represents a group of nonmetallic atoms necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring together with the N-part. Specifically, the constituent atoms or groups of the ring skeleton form a 5- to 6-membered ring skeleton configured by being selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, carbonyl groups, sulfonyl groups, and phosphonyl groups. Represents a metal atom group. Preferred Z ₁ and Z ₂ are a nonmetallic atom group forming a 5- to 6-membered ring skeleton in which the constituent atoms or groups of the ring skeleton are selected from carbon atoms, nitrogen atoms, and carbonyl groups. These may have a substituent represented by, for example, R ₂ in the above general formula (1), or may be condensed with other rings.

  Specifically, the general formula (1) includes the general formulas (2), (1-a), (1-b), (1-c), (1-d), (1-e), ( 1-f), (1-g), (1-h), (1-i) or (1-j), of which general formula (2), (1-a) , (1-b), (1-c) and (1-e) are preferred, and the general formula (2) is particularly preferred.

Wherein, R _1, R _2, R ₃ has the same meaning as R _1, R _2, R ₃ in Formula (1). R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms or substituents However, when these represent a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent represented by R ₂ . These substituents may be further substituted with the same substituent. m represents an integer of 0 to 4, and m is preferably 0 or 1. When m represents an integer greater than or equal to 2, several R < ₉ > may be the same or different.

Next, the dye represented by the general formula (2) according to the reference invention of the present invention will be described in detail.

In the general formula (2), R _1, R ₂ and R ₃ have the same meanings as R _1, R ₂ and R ₃ in formula (1). R ₅ represents a hydrogen atom or a substituent. When R ₅ represents a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent represented by R ₂ . These substituents may be further substituted with the same substituent.

In the general formula (2), R ₁ is preferably a primary alkyl group or a secondary alkyl group having 4 or less carbon atoms, preferably a methyl group or an isopropyl group, and particularly preferably a methyl group. R ₂ is preferably a hydrogen atom. R ₃ is preferably a hydrogen atom or an alkyl group. R ₅ is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ring, more preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.

Dye represented by the front following general formula (1) and (2) are respectively the following general formula (1) ', (2)' may take the structure of isomer represented by. In the reference invention of the present invention , it is described in one typical form represented by the above general formulas (1) and (2), but is different from the description of the reference invention of the present invention in the following general formula. the body also including Murrell.

Specific examples of the dye represented by the general formula (1) or (2) are shown below. Specific examples of the dye according to the present invention are 1-4, 1-22, 1-44, 1-53, 1-77 and 1-79, and other dyes are excluded from the present invention.

  Next, the metal ion-containing compound represented by the general formula (3) according to the present invention will be described in detail.

In the general formula (3), M ²⁺ represents a divalent metal ion. The metal ion represented by M ²⁺ is preferably a divalent transition metal ion selected from the group VII, Ib, IIb, IIIa, IVa, Va, VIa, and VIIa metal atoms. Specific examples include divalent metal ions of Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, and more preferable examples include divalent metal ions of Ni, Cu, Co, and Zn. preferably are two divalent metal ions der of Ni, M ²⁺ in the present invention is limited to nickel ions.

In the general formula (3), R ₂₁ and R ₂₂ represent an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₂₁ and R ₂₂ are an alkyl group, a cycloalkyl group, an aryl in the substituent which R ₁ in the general formula (1) may have. The same group as a group and a heterocyclic group can be mentioned. R ₂₁ and R ₂₂ are preferably alkyl groups.

In the general formula (3), R ₂₃ represents a hydrogen atom or a substituent. When R ₂₃ represents a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent that the group represented by R ₁ in the general formula (1) may have. Can do. These substituents may be further substituted with the same substituent. R ₂₃ is preferably a hydrogen atom, an alkyl group or an alkoxycarbonyl group, particularly preferably an alkoxycarbonyl group. In addition, when R ₂₃ represents a substituent, it may be bonded to R ₂₁ or R ₂₂ to form a ring.

  The compound represented by the general formula (3) according to the present invention may have a structure represented by the following general formula (3) ′.

_{^{Wherein, M 2+, R 21, R}} 22 and R ₂₃ has the same meaning as M ^2+, R _21, R ₂₂ and R ₂₃ in the general formula (3).

  The metal ion-containing compounds represented by the general formulas (3) and (3) ′ according to the present invention are preferably metal ion-containing compounds represented by the following general formulas (4) and (4) ′, respectively. .

In the general formula (4) and (4) ', M ²⁺ have the same meanings as M ²⁺ in the formula (3). M ²⁺ is particularly preferably are two divalent metal ions der of Ni, M ²⁺ in the present invention is limited to nickel ions. R ₂₁ has the same meaning as R ₂₁ in the general formula (3). R ₂₁ is preferably an alkyl group, and particularly preferably a methyl group.

In the general formulas (4) and (4) ′, R ₂₄ represents a hydrogen atom or a substituent. When R ₂₄ represents a substituent, the substituent is not particularly limited, and examples thereof include the same groups as the substituent that the group represented by R ₁ in the general formula (1) may have. Can do. These substituents may be further substituted with the same substituent. R ₂₄ is preferably an alkyl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group or an arylsulfonyl group, more preferably an alkyl group, an aryloxy group or an arylsulfonyl group, particularly preferably an aryloxy group or an arylsulfonyl group.

In the general formulas (4) and (4) ′, R ₂₅ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₂₅ are the alkyl group, cycloalkyl group, aryl group and heterocyclic group in the substituent which R ₁ in the general formula (1) may have. The same group as a cyclic group can be mentioned. R ₂₅ is preferably an alkyl group.

  The metal ion-containing compounds represented by (3) and (4) used in the present invention are obtained by reacting a divalent metal salt with the compounds represented by the following general formulas (3) ″ and (4) ″, respectively. can get.

Wherein, _{R 21, R 22, R 23} , R 24 and R ₂₅ have the same meanings as _{R 21, R 22, R 23} , R 24 and R ₂₅ in the general formula (3) and (4).

The method of synthesizing the metal ion-containing compound can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”. Divalent metal salts used include nickel chloride, nickel acetate, magnesium compounds represented by magnesium chloride, calcium compounds represented by calcium chloride, barium chloride, zinc chloride, zinc acetate, titanium (II) chloride, Iron chloride (II), copper chloride (II), cobalt chloride, manganese chloride (II) are mentioned, preferably nickel chloride, nickel acetate, copper chloride, copper acetate, cobalt chloride, zinc chloride, zinc acetate, most preferred Ri nickel acetate der, M ²⁺ in the present invention is limited to nickel ions. The metal ion-containing compound used in the present invention may have a neutral ligand depending on the central metal, and typical ligands include water, alcohols and amines.

  Hereinafter, although the specific example of a metal ion containing compound represented by the said General formula (3) or (4) is shown, this invention is not limited by the following specific examples.

  Hereinafter, the thermal transfer recording method of the present invention (hereinafter also referred to as thermal transfer recording method), the thermal transfer recording material of the present invention (hereinafter also referred to as thermal transfer recording material, thermal transfer sheet, dye-donating material, and ink sheet), thermal transfer. An image receiving material for recording material (hereinafter also referred to as a thermal transfer image receiving material, a thermal transfer image receiving sheet, or an image receiving sheet) will be described.

(Support)
The support used in the heat-sensitive transfer recording material of the present invention can be the same support as that used in a heat-sensitive transfer recording material having a dye-donating layer containing a conventional heat-diffusible dye, There is no particular limitation. 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, it is preferable to subject the surface to primer treatment or corona treatment.

(Dye)
In the present invention, the dye means a heat diffusible dye that can be diffused by heat from the dye-donating layer in the thermal transfer recording material and reach the dye-receiving layer in the image-receiving material. The molecular weight is preferably small. However, if the molecular weight is too small, the storage stability deteriorates, so the molecular weight is preferably 200 to 550, more preferably 250 to 500, and particularly preferably 300 to 450.

(Dye-donating layer)
In the present invention, as the heat diffusible ink contained in the dye donating layer (hereinafter also referred to as ink layer) provided on one surface of the support, at least one heat diffusible dye that can be chelated is used. The addition amount of the dye used in the present invention is usually preferably 0.05 to 20 g, more preferably 0.1 to 5 g based on 1 m ^{2 of} the ink layer described later.

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

  In order to improve the releasability with the dye image-receiving layer, a release agent may be added or a release layer may be provided. As the release agent, reactive curable silicones, phosphate ester surfactants, fluorine compounds, and the like can be used. The amount of the release agent used is preferably 0.5 to 40% by mass with respect to the solid content of the layer to be contained. When providing a release layer, the same binder as that used for the ink layer can be used.

(BC layer: also called backcoat layer, backcoating layer, 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 as a mixture. In order to further improve the heat resistance of the BC layer, a resin having a reactive group such as a hydroxyl group among the above resins may be used, and a polyisocyanate or the like may be used 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 or a separate back surface layer in contact with the BC layer to provide heat-resistant slipperiness. Good. Examples of the release agent or lubricant include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, oreganopolysiloxane, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic interfaces. Activators, 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. A preferable addition amount of the lubricant to the BC layer or the back layer is 5 to 50% by mass, particularly preferably 10 to 30% by mass, based on the total solid content of the BC layer or the back layer. The thickness of the BC layer to the back 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 faces the surface of a non-transferable resin layer (hereinafter also referred to as a non-transferable release layer), and what is a non-transferable resin layer? Post heat treatment is performed by applying heat from the opposite side.

  The non-transferable resin layer used in the present invention can be provided in the so-called surface sequential manner on the same surface as the ink layer. When the non-transferable resin layer is used alone as a sheet, the same support or BC layer or back 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 is because the dye migrates slightly to the BC layer or the back layer when stored in a roll state after coating, and the dye migrated to the BC layer or the back layer when the product is made into a small roll is a non-transferable resin layer This is performed for the purpose of preventing the phenomenon of so-called kickback, that is, re-transferring to the image. When kickback occurs, the dye retransferred to the resin layer colors the image receiving surface at the time of 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. If the thickness 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 it is less than 1%, the resin layer surface has too little unevenness and has little effect on kickback. If it exceeds 50%, the image surface after printing is roughened, and the image quality is impaired.

  In the thermal transfer recording method of the present invention, after the thermal transfer layer (dye-donating layer) of the thermal transfer recording material and the image receiving material are superposed, heat corresponding to image information is applied to the thermal transfer recording material, An image of the chelate dye formed by the reaction between the metal ion-containing compound and the chelatable heat-diffusible dye is formed on the image receiving material.

The addition amount of the metal ion-containing compound used in the present invention is usually preferably 0.05 to 50 g / m ^{2 and} more preferably 0.1 to 10 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 image receiving layer and the non-thermal transferable resin layer in the post-heating region, a release agent may be added or a separate release layer containing the release agent may be provided. As the release agent, reactive curable silicones, phosphate ester surfactants, fluorine compounds, and the like can be used. The amount of the release agent used is preferably 0.5 to 40% by mass with respect to the solid content of the layer to be contained. 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 also referred to as a protective transfer layer) used in the present invention comprises 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 protective layer include polyester resins, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, polycarbonate resins, epoxy-modified resins of these resins, resins obtained by modifying these resins with silicone, and the like. Examples thereof include a mixture of these resins, an ionizing radiation curable resin, and an ultraviolet blocking resin. Preferred resins include polyester resins, polycarbonate resins, epoxy-modified resins, and ionizing radiation curable resins. As the polyester resin, an alicyclic polyester resin in which the diol component and the acid component have one or more alicyclic compounds is preferable. 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, 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 Examples include silicone copolymers, preferably epoxy-modified acrylic, epoxy-modified polystyrene, and epoxy-modified polymers. Methacrylate 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 can be crosslinked and cured by ionizing radiation irradiation, and a photopolymerization initiator is added if necessary. And what was polymerized and bridge | crosslinked by the electron beam or the ultraviolet-ray can be used.

(UV blocking resin)
As the heat transferable protective layer, 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 to 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 is preferably provided on the support via a non-transferable release layer.

  The non-transfer release layer always has sufficient adhesion between the support and the non-transfer release layer than the adhesion between the non-transfer release layer and the thermal transfer protective layer (protective transfer layer). In order to increase the adhesive strength between the non-transferable release layer and the heat transferable protective layer before applying heat and to increase it after heat application, (1) average particles together with the resin binder Whether inorganic fine particles having a diameter of 40 nm or less are contained in an amount of 30 to 80% by mass, or (2) an alkyl vinyl ether-maleic anhydride copolymer, a derivative thereof or a mixture thereof is contained in a proportion of 20% by mass or more in total. Or (3) It is preferable to contain the 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 a portion where the support and the protective layer are in direct contact with each other is generated.

  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 other resins or fine particles may be used for the purpose of adjusting the peeling force between the release layer and the protective layer. 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 high film transparency can be obtained at the time of film formation, and any material can be used. it can. 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 of the above components (1) to (3) in a predetermined blending ratio is prepared, and the coating solution is subjected to a gravure coating method and a gravure reverse coating method. The coating layer is dried by a known technique such as The thickness of the non-transferable release layer is usually about 0.1 to 2 μm after drying.

  The thermal 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. . 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, a forgery prevention layer, a hologram layer, etc.) may be provided. . The order of the main protective layer and the other layers is arbitrary, but in general, other layers are provided between the adhesive layer and the main protective layer so that the main protective layer becomes the outermost surface of the image receiving surface of the image receiving material or image receiving sheet after transfer. Lay out the 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 should be formed of a resin having good adhesiveness when heated, such as acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyamide resin. Can do. 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 the non-transferable release layer or the support and dried. Each coating solution may be applied by a conventionally known method. An appropriate primer layer may be provided between the layers.

(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 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, cyanoacrylate-based ultraviolet absorbers, and the like. 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, 350 -400 (manufactured by Sumitomo Chemical Co., Ltd.), Mark LA-32, Mark LA- 6, Mark 1413 can be obtained from the market under the trade name (Adeka Argus Chemical Co., Ltd.) and the like, either 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 include conventionally known non-reactive ultraviolet absorbers such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines, etc., such as vinyl groups, acryloyl groups, An addition-polymerizable double bond such as acryloyl group, or those having an alcoholic hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group or the like introduced can be used. Specifically, UVA635L, UVA633L (manufactured by BASF Japan Ltd.), 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 both. 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 UV absorber. Here, the light fastening 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. In this 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 the light stabilizer include hindered amines.

  Although the usage-amount of the light-proofing agent containing said 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 a ratio of 3-10 mass parts. use. 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 added to the adhesive layer in an appropriate amount at the same time.

  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 produce a protective layer transfer sheet.

(Image-receiving sheet base material)
The image receiving sheet base material (hereinafter also referred to as a support) has a role of holding the image receiving layer and has a mechanical strength that does not hinder handling even in an overheated state because heat is applied during thermal transfer. Is preferred.

  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, polyether ether ketone, polysulfone, Examples include films of polyethersulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene-ethylene, tetrafluoroethylene-hexafluoropropylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and the like. A white opaque film formed by adding a white pigment or filler to these synthetic resins or a foamed foam sheet can be used, and is 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 the layer having fine voids, 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, particularly 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 the mixture and forming a film is preferred. In the case of those mainly composed of polyester or the like, because of their viscoelastic or thermal properties, cushioning properties and heat insulation are inferior to those mainly composed of polypropylene. Etc. are 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 to 1 × 10 ¹⁰ Pa. Moreover, 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 above-described plastic film and synthetic paper 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. The plastic film or synthetic paper may be mixed with a white pigment 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.

Also, if necessary, for the purpose of preventing curling on the side of the substrate opposite to the side where the image receiving layer is provided, resins such as polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, polycarbonate, and synthetic resins A layer of 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 Co., Ltd., and examples of the adhesive suitable for dry lamination include Takelac manufactured by Takeda Pharmaceutical Co., Ltd. A969 / Takenate A-5 (3/1), Polysol PSA SE-1400, vinylol PSA AV-6200 series manufactured by Showa High Polymer Co., Ltd., 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 a plastic film and synthetic paper as described above, or between them, or various papers and plastic film, synthetic paper, or the like are laminated, they can be bonded together with an adhesive layer.

  For the purpose of increasing the adhesive strength between the substrate and the dye image-receiving layer, various primer treatments and corona discharge treatments are preferably performed on the surface of the substrate.

(Image receiving sheet intermediate layer)
At least one or more intermediate layers may be provided between the 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. 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, but is used in the range of 100 to 300 parts by mass to improve the concealability. Further preferred.

  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 and 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 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.

  In order to prevent thermal fusing between the image receiving layer and the ink layer, a release agent is preferably added. As the release agent, phosphate plasticizers, fluorine compounds, silicone oils (including reaction curable silicones) and the like can be used, and among these, silicone oils are 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. The amount of the release agent added 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 image-receiving layer is a reverse roll coating method using a bar coater, a gravure printing method, a screen printing method, a roll coating method, a gravure plate, with a coating solution dissolved or dispersed in a solvent such as water or an organic solvent on a substrate. It can be formed by applying by an ordinary method such as air knife coating method, spray coating method, curtain coating method, extrusion coating method, and 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 directly applying the coating liquid on the substrate and drying as described above, but also having the image receiving layer formed in advance on another support, the image receiving layer on the substrate. May be transferred and formed. Further, two or more layers can be simultaneously applied to each layer, and in particular, all the layers can be applied at one time.

  The thickness of the image receiving layer is preferably about 0.1 to 10 μm as the film thickness after coating and drying.

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

(Thermal transfer recording method)
Next, an example of the thermal transfer recording method of the present invention will be described.

  An embodiment in the case where the transparent protective layer or the non-transferable resin layer is supplied in the surface order with the dye-donating layer of the thermal transfer sheet will be described with reference to the drawings. FIG. 1 is a view showing a thermal transfer sheet according to one embodiment of the present invention. In FIG. 1a, the yellow (Y), magenta (M), and cyan (C) dye-donating layer 2 is provided on the same plane of the support 3 and, in some cases, a transparent protective layer or a non-transferable resin layer is provided. It is provided sequentially.

  In FIG. 1, no gap is formed between the respective layers, but a gap may be provided as appropriate in accordance with the control method of the thermal transfer recording apparatus. Further, in order to accurately cue each layer, it is preferably provided on the detection mark thermal transfer sheet, and the method of providing is not particularly limited. Although a is provided with a dye-donating layer and a transparent protective layer or a non-transferable resin layer on the same plane of the support, it goes without saying that each may be provided on a separate support as shown in FIG. Yes. In addition, although it is the definition of a dye-donating layer, when a reactive dye is used, the dye itself contained in the dye-donating layer is a compound before the reaction, and strictly speaking, it can be said to be Y, M, and C dyes. Although not shown, Y, M, and C images are similarly expressed for the sake of convenience in the sense of layers for finally forming images.

(Thermal transfer recording device)
As the thermal transfer recording apparatus used in the present invention, for example, an apparatus as shown in FIG. 2 can be used. In FIG. 2, 10 is a thermal transfer sheet supply roll, 15 is a thermal transfer sheet, 11 is a take-up roll for winding the used thermal transfer sheet 15, 12 is a thermal head, 13 is a platen roller, 14 is a thermal head 12 and a platen roller 13. Is a thermal transfer image receiving sheet inserted between the two.

  In the thermal transfer printer according to the present invention, it is preferable that glossy tone and matte tone control can be selected in the same printer, because a printed material having a desired surface property can be obtained with one model. The selection method is not particularly limited. For example, control data corresponding to glossy tone and matte tone may be held in the thermal transfer recording apparatus, the control data selected by a simple operation of the operator may be read, and the control unit may be controlled according to the data. When a personal computer is connected to the printer, the control data may be held on the personal computer side and the selected control data may be sent to the printer by a simple operation by the operator. In addition, when heating with a heat roller, a material that alters the surface, for example, a release sheet that gives gloss, a sheet with unevenness for matting is applied to the surface of the image receiving layer after image recording. By heating with a heat roller from the back side of the sheet, recording bodies having different surfaces can be obtained.

(Post-heating method)
In the present invention, the recording material obtained by thermal transfer recording may be subjected to a heating step after image formation. Heating after image formation is performed for the purpose of fixing the transferred dye in the image receiving layer for thermal transfer recording. Examples of the heating method include a method using a thermal head used for thermal transfer recording, a method using a heat roller, a method using a heater or a hot air heater, and a method using electron beam radiation or infrared radiation.

  The recording body can be heated from both the front and back sides of the recording body or from one side, and one side or both sides are performed simultaneously, and one side or both sides are performed simultaneously.

  In the present invention, a preferable heating method is a method using a thermal head or a method using a heat roller.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

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

0.68 g of the dye according to the present invention (Exemplary dye 1-4)
Polyvinyl acetoacetal resin (KY-24, Denki Kagaku Kogyo) 1.08 g
Methyl ethyl ketone 26.4ml
Toluene 1.6ml
<Production of thermal transfer recording material>
The above ink was applied onto a polyethylene terephthalate base having a thickness of 4.5 μm using a wire bar so that the coating amount after drying was 2.3 g / m ² and dried, and a thermal transfer layer was formed on the polyethylene phthalate film. The formed thermal transfer recording material 1 was produced. The back surface of the polyethylene terephthalate base is provided with a nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) as an anti-sticking layer. In the same manner as described above, thermal transfer recording materials 2 to 13 using the dyes shown in Table 1 were prepared.

<Production of image receiving material>
The coating amount after drying an image receiving layer coating solution having the following composition on a support (including a white pigment (TiO ₂ ) and a blue tinting agent on one polyethylene layer) laminated with polyethylene laminate on both sides of paper is 7 The image receiving material 1 was prepared by coating and drying to a weight of 2 g.

<Preparation of image-receiving layer coating solution>
Metal ion-containing compound (Exemplary Compound 2-5) 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 13 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 13. The maximum density, sensitivity, and light resistance of the obtained image samples 1 to 13 were evaluated as follows.

《Maximum concentration》
The yellow 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).

"sensitivity"
The relative applied energy of each material was determined when the applied energy when the density of the image 8 formed with the thermal transfer recording material 8 was 1.0 was determined. The smaller the number, the higher the sensitivity.

《Light resistance》
About the produced sample, after measuring yellow density | concentration Ci after transcription | transfer with X-rite310TR, after irradiating 85000 lux xenon light for 1 week using the Atlas weather meter, density | concentration Cf was measured again, density | concentration 1. The dye residual ratio at 0 (Cf / Ci) × 100 was determined. Light resistance A when the dye residual ratio is 80% or more, light resistance B when it is 60% or more and less than 80%, light resistance C when it is 40% or more and less than 60%, and light resistance D when it is less than 40%. did. The above evaluation results are shown in Table 1.

  As shown in Table 1, by using the heat-sensitive transfer recording material using the dye according to the present invention, an image having high density, high sensitivity, and good light resistance can be obtained.

  Next, an image receiving material 2 having the same composition as that of the image receiving material 1 except that the metal ion-containing compound 2-5 is removed from the image receiving material 1 is prepared, and the image receiving surface of the image receiving material 2 and each of the image samples 1 to 13 are overlapped. At the same time, a load of 196 Pa was applied at 40 ° C. and left for 3 days, and then peeled off to visually observe the degree of transfer of the dye to the image receiving material 2.

  As a result, none of the images 1 to 6 recorded by the thermal transfer recording method of the present invention showed dye transfer to the image receiving material 2, but image samples 8 and 9 showed some dye transfer, In 7 and 10-13, a great amount of dye transfer was observed. That is, it can be seen that an image having excellent fixability can be obtained according to the thermal transfer recording method of the present invention.

Example 2
[Preparation of thermal transfer sheet 1]
(Support A with back coat layer)
A back coat layer coating solution 1 having the following composition is applied on one surface of a 4.5 μm thick polyethylene terephthalate film with an easy-contact layer (Lumirror manufactured by Toray Industries, Inc.) by a gravure coating method, dried, and then heat-cured. Then, a support A having a back coat layer having a dry film thickness of 1.0 μm was produced.

<Preparation of backcoat layer coating solution 1>
Polyvinyl butyral resin (S-LEC BX-1 manufactured by Sekisui Chemical Co., Ltd.)
3.5 parts by mass Phosphate ester surfactant (Pricesurf A208S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
3.0 parts by mass Phosphate ester surfactant (Phosphanol RD720 manufactured by Toho Chemical Co., Ltd.)
0.3 parts by mass Polyisocyanate (Dainippon Ink & Chemicals, Barnock D750-45)
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-donating layer and protective transfer layer)
Each dye-donating layer formed on the surface opposite to the backcoat surface of the support A with the backcoat layer using a yellow dye coating liquid 1, a magenta dye coating liquid 1, and a cyan dye coating liquid 1 having the following composition: (Dry film thickness is 1 μm) and a multi-layer protective transfer layer (non-transfer release layer / protective layer / adhesive layer three-layer structure) are provided in the surface order as shown in FIG. A thermal transfer sheet 1 was produced.

<Yellow dye coating solution 1>
Yellow pigment: Exemplified pigment 1-3 4.5 parts by mass Polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS-5)
5.0 parts by mass Urethane-modified silicone resin (Dairoma SP-2105, 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 <Magenta dye coating solution 1>
Magenta dye MA 4.0 parts by mass Polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS-5)
5.5 parts by mass Urethane-modified silicone resin (Dairoma Seika SP-2105, 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 <Cyan dye coating solution 1>
Cyan dye CY 4.0 parts by mass Polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS-5)
5.5 parts by mass Urethane-modified silicone resin (Dairoma Seika SP-2105, 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

(Non-transferable release layer)
A non-transferable release layer coating solution 1 having the following composition was coated 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 Deionized water 3.0 parts by mass Denatured ethanol 10 parts by mass (Protective transfer layer)
A protective transfer layer coating solution 1 having the following composition is applied onto the formed non-transferable release layer by the gravure coating method and dried so that the solid content is 2.0 g / m ^2, and then protected. A transfer layer was formed.

<Protective transfer layer coating solution 1>
Acrylic resin 15 parts by weight Vinyl chloride-vinyl acetate copolymer 5 parts by weight Copolymerized resin (UVA-635L manufactured by BASF Japan Ltd.) with reactive UV absorber 40 parts by weight Polyethylene wax 0.3 part by weight Polyester resin 0 .1 part by weight Methyl ethyl ketone 40 parts by weight Toluene 40 parts by weight Zinc antimonate (Sellnax manufactured by Nissan Chemical Co., Ltd.) 20 parts by weight (adhesive layer)
On the protective transfer layer thus formed, an adhesive layer coating solution 1 having the following composition was applied by a gravure coating method and dried so as to have a solid content of 2.0 g / m ^2, and dried to form an adhesive layer. .

<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 A multilayer constitution protective transfer layer, which is a laminate of a protective transfer layer and an adhesive layer, was prepared on a non-transferable release layer. .

[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 thermal transfer image-receiving sheet, coated paper (US basis weight 157 g / m ² OK Topcoat S, manufactured by Oji Paper Co., Ltd.) was used. , High density polyethylene (J-Rex LZ0139-2, density 0.952, manufactured by Nippon Polyolefin Co., Ltd.) blended with 15% by mass of an ethylene-α olefin copolymer (Tuffmer A-4085, Mitsui Petrochemical Co., Ltd.) Is abbreviated as HDPE) and polypropylene (J-Allomer LR711-5, density 0.905, manufactured by Nippon Polyolefin Co., Ltd., hereinafter abbreviated as PP) by a co-extrusion coating method using a known multilayer T die, Two layers were coextruded and laminated so as to be in contact with each other. Further, after the corona discharge treatment is applied to the outer PP surface, 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, and the support is then applied. Produced. 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 (BR-85 manufactured by Mitsubishi Rayon Co., Ltd.) 19.8 parts by weight Nylon filler (MW-330 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 On the other hand As a resin layer having fine voids, a foamed polypropylene sheet (35 MW846 Mobile Plastics Europe) having a thickness of 35 μm was used, and an intermediate layer coating solution and a dye image receiving layer coating solution having the following composition were formed on one surface thereof. Were coated and dried sequentially by a gravure reverse coating method so that the coating film thickness when dried was 1 μm and 3 μm, respectively, to produce a foamed polypropylene sheet in which an intermediate layer and a dye image-receiving layer were laminated.

  Next, the surface 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 surface of the support on which the back resin layer is not provided (coated paper surface) are described below. A thermal transfer image-receiving sheet 1 was prepared by laminating with an adhesive having a 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 Fluorescent whitening agent (Ubitex OB, manufactured by Ciba Geigy Japan) 0.2 Part by weight Isocyanate (Takenate A-14, Takeda Pharmaceutical Company Limited) 2.0 parts by weight Methyl ethyl ketone 15.5 parts by weight Toluene 15.5 parts by weight Isopropyl alcohol 7.7 parts by weight <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 (Denkarac # 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 Metal ion-containing compound (Exemplary) Compound 2-5) 8.0 parts by mass Vinyl-modified silicone (X-62-1212 manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 parts by mass Catalyst: CAT PLR-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by mass Catalyst: CAT PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.2 parts by mass Solvent: 39.0 parts by mass of methyl ethyl ketone Solvent: 39.0 parts by mass of toluene << Preparation of Print Sample >>
Using the produced thermal transfer sheet 1 and thermal transfer image receiving sheet 1, yellow and magenta with gradation values that are sequentially increased every 15 gradations using a sublimation thermal transfer printer (RC-602 type manufactured by Konica Minolta Photo Imaging). , Cyan, and neutral (yellow, magenta, and cyan three-color overlap) step patterns were transferred, and then a transparent protective layer was transferred onto the image to produce a print sample.

  When the obtained image sample was evaluated in the same manner as in Example 1, an image having high density, high sensitivity, and excellent light resistance and fixability could be obtained.

Example 3
It replaced with the exemplary metal ion containing compound 2-5 in Example 2, and only having used equal mass exemplary metal ion containing compound 2-10, exemplary metal ion containing compound 2-11, and exemplary metal ion containing compound 2-12. As a result, the effects of the present invention were confirmed.

It is a top view which shows the example of the aspect of the pigment | dye donor layer provided in the thermal transfer sheet used for the method of this invention, and a reheating process layer. It is a conceptual diagram of an example of the thermal transfer recording apparatus used for the method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Protection layer area | region 2Y Area | region containing yellow dye 2M Area | region containing magenta dye 2C Area | region containing cyan dye 3, 3 'Thermal transfer sheet support 10 Thermal transfer sheet supply roll 11 Winding roll 12 Thermal head 13 Platen roller 14 Thermal transfer Image receiving sheet 15 Thermal transfer sheet

Claims (2)

A thermal transfer recording material having a dye-donating layer containing at least one of the following dyes 1-4, 1-22, 1-44, 1-53, 1-77 and 1-79 on a support; And an image receiving material having a dye image receiving layer containing a metal ion-containing compound represented by the following general formula (3) to form a metal chelate dye image having high density, high sensitivity and light resistance. A thermal transfer recording material, characterized by being.

[ Wherein M ²⁺ represents a nickel ion, R ₂₁ and R ₂₂ represent an alkyl group, a cycloalkyl,
Represents a hydrogen group, an aryl group or a heterocyclic group, and R ₂₃ represents a hydrogen atom or a substituent. When R ₂₃ represents a substituent, it may be bonded to R ₂₁ or R ₂₂ to form a ring. ] The heat-sensitive transfer recording material having a dye-providing layer containing at least one of the following dyes 1-4,1-22,1-44,1-53,1-77 and 1-79 on a support, on a support An image receiving material having a dye image-receiving layer containing a metal ion-containing compound represented by the following general formula (3) is superimposed on the heat-sensitive transfer recording material according to image information, and the dye is transferred to the dye image-receiving layer. And a metal chelate dye image having high density, high sensitivity and light resistance is formed in the image receiving material by the reaction between the dye and the metal ion-containing compound.

[Wherein, M ²⁺ represents a nickel ion, R ₂₁ and R ₂₂ represent an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R ₂₃ represents a hydrogen atom or a substituent. When R ₂₃ represents a substituent, it may be bonded to R ₂₁ or R ₂₂ to form a ring. ]

Images