JP2005088332A - Thermosensitive transfer recording material, thermosensitive recording method, color toner, optical recording medium and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosensitive transfer recording material including a new coloring material having hues desirable on color reproducibility and favorable light resistance, a thermosensitive transfer method, color toners, an optical recording medium and color filters. <P>SOLUTION: This thermosensitive transfer recording material includes at least one kind of coloring matters expressed by general formula (1): X=D-B, wherein at least either X or B is substituted with at least one kind of hydrogen-bonding groups selected from the group consisting of -OH, -NHSO<SB>2</SB>Rb, -NHCOORb, -NHCONHRb and -NHCORc. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermal transfer recording material containing a specific dye, a thermal transfer recording method, a color toner, an optical recording medium, and a color filter.

  Azomethine dyes are widely used in various colors such as yellow, red, magenta, blue and cyan. In recent years, it has been increasingly applied to various applications such as thermal transfer recording materials, color toners, optical recording media, and color filters.

  The thermal transfer recording has advantages such as easy operation and maintenance, downsizing and cost reduction of the apparatus, and low running cost. Proposal of thermal transfer recording material and image forming method using heat diffusible dye (hereinafter referred to as chelate dye) that can be chelated for the purpose of improving the stability of the image obtained by thermal transfer recording, especially fixing property and light resistance. For example, they are described in JP-A-59-78893 (Patent Document 1), 59-10349, and 60-2398. The chelate dye disclosed in the patent is a metal chelate dye formed by bidentate or tridentate coordination with a metal ion using an azo dye as a ligand. Images formed using these chelate dyes are excellent in light resistance and fixability, but are not fully satisfactory in terms of the sensitivity of the thermal transfer recording material and the storage stability of the material itself, and further improvements are desired. It was rare.

  In the case of using the coloring matter in a color toner, in a color copier or color laser printer using an electrophotographic method, a colorant is generally dispersed in a resin particle or a toner in which a colorant is dispersed in a resin particle. Adhered toner is used. Since the method of attaching a coloring material to the resin surface is coloring only the surface, it is difficult to obtain a sufficient coloring effect. Further, there are problems that the charging performance changes due to separation from the surface of the colorant, and the surface of the fixing roller is contaminated. Therefore, a toner in which a coloring material is dispersed inside a particle is widely used. The performance required for such a color toner includes color reproducibility, image transparency in an Over Head Projector (hereinafter referred to as OHP), and light resistance. Toners in which pigments are dispersed in particles as a colorant are disclosed in JP-A-62-157051, JP-A-62-255556 and JP-A-6-118715 (Patent Document 2). Is excellent in light resistance, but it is insoluble, so it easily aggregates, and problems such as a decrease in transparency and a change in the hue of the transmitted color are problematic. On the other hand, toners using dyes as colorants are disclosed in JP-A-3-276161 (Patent Document 3), JP-A-2-207274, and JP-A-2-207273. Although it is highly transparent and has no hue change, it has a problem with light resistance.

  In recent years, with the rapid increase in the amount of information, large capacity optical recording media have attracted attention. An organic optical recording medium that can easily and densely record information with an inexpensive semiconductor laser uses a long-wavelength absorbing dye that absorbs light in the red to near-infrared region. Conventionally, cyanine dyes with excellent absorption and reflection characteristics have been used for this purpose among various dyes. However, since storage stability such as light resistance is inferior, information is lost or cannot be written over time. It was. In order to solve such problems, for example, U.S. Pat. Nos. 3,432,300, 4,050,938, JP-A-60-118748, 63-199248, JP-A-2- Although a light stabilizer or a light stabilization method is described in Japanese Patent Publication No. 3000028 (Patent Document 4) or the like, sufficient storage stability has not been obtained.

In addition, since the color filter is required to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a dyeable photosensitive material is applied to a substrate such as glass, followed by pattern exposure of one filter color, and the unexposed portion is washed away in the development process, and the remaining pattern portion is dyed with the filter color. A color filter can be manufactured by sequentially repeating the operation such as dyeing for all filter colors (see Patent Document 5). This method uses dyes and has high transmittance and excellent optical characteristics of the color filter, but there is a limit to light resistance, heat resistance, etc., and a color material with excellent various resistances and high transparency is desired. It was. Thus, organic pigments having excellent light resistance and heat resistance have been used instead of dyes, but it has been difficult to obtain optical properties like dyes with color filters using pigments.
JP 59-78893 A JP-A-6-118715 JP-A-3-276161 JP-A-2-300288 Japanese Patent Laid-Open No. 5-80213

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermal transfer recording material, a thermal transfer recording method, and a novel dye having a favorable hue in terms of color reproducibility and having good light resistance. To provide a color toner, an optical recording medium, and a color filter.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
A thermal transfer recording material comprising at least one dye represented by the following general formula (1).

General formula (1)
X = D-B
[Wherein, X represents a group represented by the following general formulas (1-1) to (1-4). D represents a nitrogen atom or ═CR ₁ —, and R ₁ represents a hydrogen atom or a substituent. B represents a group represented by the following general formulas (2-1) to (2-4). However, at least one of X and B has at least one hydrogen bonding group selected from —OH, —NHSO ₂ Rb, —NHCOORb, —NHCONHRb, and —NHCORc, Rb represents a substituent, and Rc represents Represents an aryl group, a heterocyclic group or a branched alkyl group. ]

[Wherein R ₂ , R ₃ or Ra represents a hydrogen atom or a substituent. Z represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a substituent, and the nitrogen-containing heterocyclic ring may form a condensed ring with another ring. ]]
(Claim 2)
2. The thermal transfer recording material according to claim 1, wherein X in the general formula (1) is represented by the general formula (1-2).
(Claim 3)
The thermal transfer recording material according to claim 1 or 2, wherein B in the general formula (1) is represented by the general formula (2-1).
(Claim 4)
At least one of X and B in the general formula (1) has a hydrogen bonding group, and the hydrogen bonding group is represented by the general formula (1-1) to the general formula (1-4) or the general formula (2-1). The thermal transfer recording according to any one of claims 1 to 3, which is hydrogen-bonded to a nitrogen atom or an oxygen atom on the heterocyclic ring of the group represented by formula (2-4). material.
(Claim 5)
The hydrogen bonding group is —OH or —NHSO ₂ Rb (wherein Rb has the same meaning as Rb in the case of the general formula (1)). The thermal transfer recording material described.
(Claim 6)
A heat-sensitive transfer recording material comprising at least one dye represented by the following general formula (2).

[Wherein R ₂ represents a hydrogen atom or a substituent. D represents a nitrogen atom or ═CR ₁ —, and R ₁ represents a hydrogen atom or a substituent. B represents a group represented by the general formulas (2-1) to (2-4). R ₇ and R ₈ represent a substituent, and R ₉ represents a hydrogen atom or a substituent. ]
(Claim 7)
The thermal transfer recording material according to claim 6, wherein B in the general formula (2) is represented by the general formula (2-1).
(Claim 8)
In the general formula (2), at least one of R ₂ , R ₇ , R ₉ or B is —OH, —NHSO ₂ Rb, —NHCOORb, —NHCONHRb, —NHCORc (where Rb and Rc are represented by the general formula (1)) The thermal transfer recording material according to claim 6 or 7, which has at least one hydrogen-bonding group selected from the group consisting of Rb and Rc in the above case.
(Claim 9)
An image-receiving material is superimposed on a heat-sensitive transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) or (2) on the support, and the heat-sensitive transfer recording material is used as image information. A heat-sensitive transfer recording method, wherein an image is formed on the image-receiving material by heating in response.
(Claim 10)
A heat-sensitive transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) or (2) on a support, and a dye image-receiving layer containing a metal ion-containing compound on the support. A thermal transfer recording material, wherein the thermal transfer recording material is heated in accordance with 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. Recording method.
(Claim 11)
A color toner comprising at least one dye represented by the general formula (1) or (2).
(Claim 12)
An optical recording medium comprising at least one dye represented by the general formula (1) or (2).
(Claim 13)
A color filter comprising at least one dye represented by the general formula (1) or (2).

  According to the present invention, there are provided a thermal transfer recording material, a thermal transfer recording method, a color toner, an optical recording medium, and a color filter which contain a novel dye having a hue favorable for color reproducibility and good light resistance. Can do.

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

  First, the pigment | dye which concerns on this invention is explained in full detail. In the general formula (1), X represents the general formulas (1-1) to (1-4), and B represents the general formulas (2-1) to (2-4).

R ₂ , R ₃ or Ra represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group (an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an isopropyl group). , T-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, etc.), aralkyl group (for example, Benzyl group, 2-phenethyl group, etc.), aryl group (eg phenyl group, p-tolyl group, p-methoxyphenyl group, o-chlorophenyl group, m- (3-sulfopropylamino) phenyl group, etc.), heterocyclic A group (for example, 2-pyridyl group, 2-thienyl group, 2-furyl group, imidazolyl group, pyrazolyl group, etc.), Lucoxy group (C1-C12 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, 3-carboxypropoxy group, etc.), aryloxy group (such as phenoxy group, p-methoxy group) Phenyl group, o-methoxyphenoxy group, etc.), acylamino group (eg acetylamino group, propionylamino group, benzoylamino group, 3,5-disulfobenzoylamino group etc.), sulfonylamino group (eg methanesulfonylamino group, benzene) Sulfonylamino group, 3-carboxybenzenesulfonylamino group, etc.), ureido group (eg 3-methylureido group, 3,3-dimethylureido group, 3-phenylureido group etc.), alkoxycarbonylamino group (eg ethoxycarbonylamino group) etc) An alkylthio group (eg, methylthio group, ethylthio group, etc.), an arylthio group (eg, phenylthio group, p-tolylthio group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), a carbamoyl group (eg, methylcarbamoyl group, Dimethylcarbamoyl group etc.), sulfamoyl group (eg dimethylsulfamoyl group, di- (2-hydroxyethyl) sulfamoyl group etc.), sulfonyl group (eg methanesulfonyl group, phenylsulfamoyl group etc.), acyl group (acetyl group) Benzoyl group, etc.), cyano group, and amino group (for example, methylamino group, diethylamino group, etc.), sulfonic acid group (or salt thereof), carboxylic acid group (or salt thereof). They may further have a substituent.

  Z represents a group of atoms forming a nitrogen-containing heterocyclic ring which may have 5 or 6-membered substituents. Specific examples of the heterocyclic ring include pyrrole, pyrazole, imidazole, triazole, thiadiazole, oxazole and thiazole. , Pyran, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, benzothiophene, benzimidazole, benzothiazole, benzoxazole, purine, quinoline, isoquinoline, coumarin, chromone, 3H-pyrrole, 3H-pyrrolidine, oxazolidine, imidazolidine, Examples of the ring include thiazolidine, 3H-indole, indandione, barbitur, pyrazoloazole, imidazoazole, and pyrroloazole. Pyridine, pyrimidine, pyrazole, triazole, imidazole, oxazole, pyrrole, 3H-indole and the like are preferable. These rings may form a condensed ring with another carbocyclic ring (such as a benzene ring) or a heterocyclic ring (such as a pyridine ring). Examples of the substituent that the ring may have include the same groups as those described above, but preferably an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a nitro group, a cyano group, Examples include an acylamino group, an alkoxy group, a hydroxyl group, an alkoxycarbonyl group, a sulfonic acid group, a carboxylic acid group, a halogen atom, and the like, and these groups may be further substituted.

  X preferably represents the general formula (1-2), and B preferably represents the general formula (2-1).

D represents a nitrogen atom or ═CR ₁ —, R ₁ represents a hydrogen atom or a substituent, and the substituent is a substitution in the case of R ₂ , R ₃ , or Ra in the general formula (1-2). Synonymous with group.

  The group represented by the general formula (2-1) according to the present invention may have a structure such as the following general formula (2-1a) which is a tautomer.

Wherein, R _2, R _3, and Ra have the same meanings as R _2, R _3, and Ra in the general formula (2-1).

In the present invention, the hydrogen-bonding group is —OH, —NHSO ₂ Rb (Rb represents a substituent. The substituent is a substituent in the case of R ₂ , R ₃ , Ra in the general formula (1-2). And preferably include an alkyl group, an aryl group, a heterocyclic group, etc.), —NHCOORb (Rb is as defined above), —NHCONHRb (Rb is as defined above), —NHCORc (Rc is aryl) Represents a group, a heterocyclic group or a branched alkyl).

  Rc represents an aryl group, a heterocyclic group or a branched alkyl group, preferably an aryl group or a heterocyclic group, and more preferably an aryl group.

The hydrogen bonding group preferably represents —OH or —NHSO ₂ Rb.

In the general formula (2), R ₂ and R ₉ represent a hydrogen atom or a substituent, and R ₇ and R ₈ represent a substituent. Examples of the substituent include R _{2 in the} general formula (1-2). , R ₃ and Ra have the same meaning as the substituent.

D is a nitrogen atom or = CR ₁ - represents a. R ₁ represents a hydrogen atom or a substituent, and the substituent has the same meaning as the substituent in the case of R ₂ , R ₃ , and Ra in the general formula (1-2).

  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.

  Below, the synthesis example of the pigment | dye represented by General formula (1) and General formula (2) is shown.

  Synthesis Example 1 (Synthesis of Exemplified Dye D-9)

A 300 ml eggplant type flask was charged with 5 g of compound (A), 5.6 g of compound (B), 160 ml of toluene, and 2.2 g of N, N′-dicyclohexylcarbodiimide (DCC), and heated under reflux for 8 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, insolubles were removed, and the filtrate was concentrated and purified by column chromatography. Further, recrystallization was performed with acetonitrile to obtain 7.2 g (yield 67%) of the target product.
It was confirmed to be the target product by NMR and mass spectrum.

  Synthesis Example 2 (Synthesis of Exemplified Dye D-26)

A 300 ml eggplant type flask was charged with 4 g of compound (C), 3.6 g of compound (D), 2.5 g of morpholine, and 150 ml of toluene, and heated under reflux for 10 hours. After completion of the reaction, the reaction solution was concentrated. This was purified by column chromatography, and the resulting crude crystals were recrystallized from ethyl acetate to obtain 3.3 g (yield 45%) of the desired product D-26.
It was confirmed to be the target product by NMR and mass spectrum.

  Other dyes can be easily synthesized according to the above synthesis method.

  The thermal transfer recording material (hereinafter also referred to as a thermal transfer sheet) of the present invention will be described below.

(Support)
The support used in the heat-sensitive transfer recording material of the present invention can be the same support as that used in conventional thermal transfer sheets, and is not particularly limited. Specific examples of preferable 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 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 above-mentioned support is poorly adhered to the ink layer formed on this surface, it is preferable to subject the surface to primer treatment or corona treatment.

(Ink layer)
In the present invention, as the heat diffusible ink contained in the ink layer provided on one surface of the support, at least one dye represented by the general formula (1) or the general formula (2) of the present invention is used.

The addition amount of the coloring matter 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 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. 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)
It is preferable to provide a BC layer (back coating 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 back 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 back layer is 5 to 50% by mass, particularly preferably 10 to 30% by mass, based on the total solid content of the back layer. The thickness of 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, after the dye transfer, the transferred surface and the surface of the non-transferable resin layer face each other, and heat is applied by applying heat from the opposite side of the non-transferable resin layer. Process.

  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 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 means that when stored in a roll state after application, the dye migrates slightly to the back layer, and when the product is in a small volume, the dye migrated to the back 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 0.1 μm or less, the resin layer surface has too little unevenness and has no effect on kickback, and if it is 50 μm or more, 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 1% or less, the resin layer surface has too little unevenness and has little effect on kickback, and if it is 50% or more, the image surface after printing is roughened and the image quality is impaired.

In the present invention, the resin layer may contain a metal ion-containing compound, and examples of the metal ion-containing compound include inorganic or organic salts and metal complexes of metal ions, among which organic acid salts and complexes are preferable. . Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table. Among them, Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti And Zn are preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable. 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.

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.

  Further, in order to improve the releasability between the image receiving layer and the non-heat transferable resin layer in the post-heating region, 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. 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 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 No. 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 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. As the ionizing radiation curable resin, known ones can be used. For example, a radical polymerizable polymer or oligomer is crosslinked and cured by ionizing radiation irradiation, and a photopolymerization initiator is added if necessary, and an electron beam Those obtained by polymerization and crosslinking with ultraviolet rays can be used.

(UV blocking resin)
The main purpose of the protective layer containing the ultraviolet blocking resin is to impart light resistance to the printed material. As the ultraviolet blocking resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber with a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, 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 via a non-transferable release layer.

  The non-transferable release layer always makes the adhesive force between the support and the non-transferable release layer sufficiently higher than the adhesive force between the non-transferable release layer and the thermal transfer protective layer, and For the purpose of increasing the adhesive force between the non-transferring release layer and the heat transferable protective layer before applying heat to that after applying heat, (1) together with the resin binder, the average particle size Contains 30 to 80% by mass of inorganic fine particles of 40 nm or less, or (2) contains an alkyl vinyl ether-maleic anhydride copolymer, a derivative thereof, or a mixture thereof in a total proportion of 20% by mass or more. Or (3) It is preferable that the ionomer is contained 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 the thickness exceeds 40 nm, the unevenness of the surface of the heat transferable protective layer increases due to the unevenness of 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 is generated. .

  Examples of the alkyl vinyl ether-maleic anhydride copolymer or derivatives thereof 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 alcohol (for example, methanol, ethanol, etc.). , Propanol, isopropanol, butanol, isobutanol and the like) 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, 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 thermal transferable protective 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, 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 usually other layers are arranged between the adhesive layer and the main protective layer so that the main protective layer becomes the outermost surface of the image receiving surface after transfer. .

  An 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>
It is preferable that at least one layer of the heat transferable protective layer contains an ultraviolet absorber, but when it is contained in the transparent resin layer, the transparent resin layer is present on the outermost surface of the printed matter after transfer of the protective layer. The heat sensitive adhesive layer is particularly preferred because the effect is reduced over time due to the influence of the environment over a long period of time.

  Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based ultraviolet absorbers, and the like. , 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-3 , It can be obtained from the market under the trade names such as Mark 1413 (Adeka Argus Chemical Co., Ltd.), both 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 salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines and other non-reactive ultraviolet absorbers such as vinyl groups and acryloyl groups, 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 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 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 degradation of the dye by absorbing or blocking the alteration or degradation of the dye, such as light energy, thermal energy, and oxidation. 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 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.

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 transparent resin layer of the protective layer transfer sheet may be provided alone on the support, or may be provided in the surface order with the ink layer of the thermal transfer sheet.

(Image-receiving sheet base material)
The image receiving sheet base material has a role of holding the image receiving layer, and heat is applied during thermal transfer. Therefore, it is preferable that the image receiving sheet base material has a mechanical strength that does not hinder handling even in an overheated state.

  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 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, 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 configurations, all layers constituting the layer may contain fine voids, or a layer having 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.

Further, if necessary, a resin such as polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, polycarbonate, or the like is provided on the surface of the substrate opposite to the side on which the image receiving layer is provided for the purpose of preventing curling. Or a layer of synthetic paper. 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. Examples include 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 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 thermal transfer image receiving layer and the ink jet 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 intermediate layer may be provided between the image receiving layer and the image receiving sheet base material. 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, and an antistatic layer. 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 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 dye is easy to dye. 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 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 image receiving layer is a reverse roll using a bar coater, a gravure printing method, a screen printing method, a roll coating method, a gravure plate, 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 ordinary methods such as a coating method, an air knife coating method, a spray coating method, a curtain coating method, an extrusion coating method, and the like, 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 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 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.

  As the binder resin for the color toner of the present invention, all commonly used binders can be used. For example, styrene resin-acrylic resin-styrene / acrylic resin-polyester resin and the like can be mentioned.

  In the present invention, inorganic fine powder and organic fine particles may be externally added to the color toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. In addition, those having a number average primary particle diameter of 10 to 500 nm are preferable, and further 0.1 to 20% by mass is preferably added to the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene-low molecular weight polyethylene-ethylene-propylene copolymer, microcrystalline wax-carnauba wax-sazole wax-paraffin wax, and the like. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron-ferrite or a resin-coated carrier whose surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the color toner of the present invention is applied is not particularly limited. For example, a method of forming an image by repeatedly forming a color image on a photoconductor and then transferring it, or forming on a photoconductor Examples include a method of sequentially transferring the formed image to an intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.

  The substrate constituting the optical recording medium of the present invention is required to be substantially transparent (transmittance of 80% or more) in the wavelength region (350 to 900 nm) of laser light used for recording and reproduction. Examples of the material constituting the substrate include polymethyl methacrylate resin, acrylic resin, polycarbonate resin, epoxy resin, polysulfone resin, transparent resin such as methylpentene polymer, and glass. In addition, an oxygen barrier film may be formed on the outer surface, inner surface, and inner-outer peripheral surface of the substrate as necessary. Further, it is preferable that a tracking groove is formed on the substrate on which the recording layer is formed.

  In the recording layer using the dye of the present invention, the extinction coefficient k in the wavelength region of the laser beam becomes preferable as the recording layer of the optical recording medium, and the light absorption property suitable for recording and the reflection suitable for reproduction. Combined with rate. Here, when the extinction coefficient k of the recording layer in the wavelength region of the laser beam is excessive, the reflectance is lowered, and reproduction by reflected light cannot be performed sufficiently satisfactorily. When the extinction coefficient k is too small, it becomes difficult to perform recording with a normal recording power. The extinction coefficient k is preferably 0.01 to 0.1. On the other hand, the refractive index n (real part of the complex refractive index) of the recording layer in the wavelength region of the laser light is preferably 1.8 to 4.0.

  The recording layer constituting the optical recording medium of the present invention may contain other types of dye compounds, various resins, surfactants, antistatic agents, dispersants, antioxidants, crosslinking agents, and the like. Good.

  The recording layer may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate.

  The method for forming the recording layer on the substrate is not particularly limited, for example, spin coating method, dip coating method, spray coating method, blade coating method, roller coating method, bead coating method, Meyer coating method, Various methods such as a curtain coating method can be applied. Examples of the solvent used for forming the recording layer include ketone solvents such as cyclohexanone, ester solvents such as butyl acetate, ether solvents such as ethyl cellosolve, alcohol solvents, aromatic solvents such as toluene, and halogenated compounds. Examples thereof include alkyl solvents.

A reflective layer may be formed on the recording layer. The reflective layer can be formed by means such as vapor deposition or sputtering using a metal having high reflectivity such as Au, Al—Mg alloy, Al—Ni alloy, Ag, Pt, and Cu.
On the reflective layer, a protective film made of, for example, an ultraviolet curable resin may be formed.

  An adhesive layer may be provided between the recording layer and the reflective layer to bring them into close contact.

  When the dye of the present invention is used for color filters, when dispersing the dye of the present invention in a transparent resin, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used.

  In the present invention, as a resin varnish for dispersing a pigment to obtain a colored composition, a varnish used in a conventionally known colored composition for a color filter is used. As the dispersion medium, a solvent suitable for the resin varnish or an aqueous medium is used. Further, conventionally known additives such as a dispersion aid, a smoothing agent and an adhesion agent are added and used as necessary.

  As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish are photosensitive resin varnishes used for ultraviolet curable inks, electron beam curable inks, etc., and non-photosensitive resin varnishes include, for example, relief printing inks, planographic inks, intaglio gravure inks, Any of varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, and varnishes used for thermal transfer ribbons can be used.

  Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples of the varnish include a polyester acrylate resin, a polyepoxy acrylate resin, a polyurethane acrylate resin, a polyether acrylate resin, and a polyol acrylate resin, and a varnish to which a monomer is added as a reactive diluent. The photosensitive coloring composition of the present invention can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the pigment of the present invention and the varnish, and then bricking it by a conventionally known method. Moreover, it can replace with said photoinitiator and can use it as a thermopolymerizable coloring composition using a thermal polymerization initiator. When forming a color filter pattern using the above photosensitive coloring composition, spin coating the photosensitive coloring composition on a transparent substrate, coating the entire surface using a low-speed rotary coater, roll coater, knife coater, etc. Or performing full printing by various printing methods or partial printing that is slightly larger than the pattern, and after pre-drying, the photomask is brought into close contact, and exposure is performed using an ultrahigh pressure mercury lamp to print the pattern. Next, development and washing are carried out, and post-baking is carried out as necessary to form a color filter pattern.

  Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, amino resin modified polyester resins Resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethyl cellulose, styrene-maleic acid ester copolymer water-soluble Water-soluble salts of (meth) acrylic acid ester (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, etc., used alone or in combination Is done.

  When forming a color filter pattern using the above-mentioned non-photosensitive coloring composition, the non-photosensitive coloring composition, for example, the above-described various printing methods using a printing ink for color filters is used on a transparent substrate. A method of printing a colored pattern directly on a substrate, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for color filters, an electronic printing method or an electrostatic printing method, or Examples thereof include a method in which a colored pattern is once formed on a transferable substrate by the above-described method and then transferred to a color filter substrate. Then, according to a conventional method, baking is performed as necessary, polishing for smoothing the surface, or top coating for protecting the surface is performed. Further, a black matrix is formed according to a conventional method to obtain an RGB color filter.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1 (thermal recording material)
<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 dye of the present invention was good, and the inkability was also good.

Pigment of the present invention (D-1) 0.68 g
Polyvinyl acetoacetal resin (KY-24, manufactured by Denki Kagaku Kogyo)
1.08g
Methyl ethyl ketone 26.4ml
Toluene 1.6ml
<Production of thermal transfer recording material>
The above ink is applied and dried on a 4.5 μm thick polyethylene terephthalate base 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 a silicon | silicone modified urethane resin (SP-2105, Dainichi Seika) as a sticking prevention layer.

In the same manner as described above, thermal transfer recording materials 2 to 10 using the dyes shown in Table 1 were prepared.
<Production of image receiving material>
The coating amount after drying a 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 7.2 g. Thus, the image receiving material 1 was prepared by coating and drying.

Metal ion-containing compound (M-1) 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>
The thermal transfer recording material and the image receiving material 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 an image sample.

  The maximum density of the obtained image sample, the sensitivity of the thermal transfer recording material, the light fastness of the image, and the color reproducibility 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 was determined when the applied energy when the density of the image formed with the thermal transfer recording material 9 was 1.0 was determined. The smaller the number, the higher the sensitivity.

<Light resistance>:
The obtained image was irradiated with light with a xenon fade meter for 5 days to evaluate light resistance.

  Table 1 shows the results of the compound remaining rate after the light irradiation.

The compound residual ratio represents the density before irradiation D _0, the density after light irradiation D / D ₀ × 100 as D.

《Color reproducibility》
The color tone of the obtained image was visually evaluated. Vivid colors by visual evaluation with 10 monitors
Dull color ... △
Dirty color
Evaluation was performed in three stages.

  The results are shown in Table 1.

  As shown in Table 1, the heat-sensitive transfer recording material using the compound of the present invention can obtain an image with high density and good image storage stability (light resistance) and color reproducibility.

Example 2 (color toner)
<Production of color toner>
100 parts of a polyester resin, the number of parts of the colorant shown below, and 3 parts of polypropylene were mixed, kneaded, pulverized, and classified to obtain a powder having an average particle diameter of 8.5 μm. Further, 100 parts of this powder and 1.0 part of silica fine particles (particle diameter 12 nm, hydrophobization degree 60) were mixed with a Henschel mixer to obtain color toners 201 to 209.

Colorant Number of parts added to colorant Dye of the present invention (described in Table 2) 4 parts Dye for comparison (described in Table 2) 8 parts << Production of Carrier >>
High-speed 1960 g of Cu-Zn ferrite particles having a saturation magnetization of 25 emu / g when an external magnetic field of 40 g of styrene / methyl methacrylate = 6/4, specific gravity of 5.0, mass average diameter of 45 μm, and 1000 oersted is applied. The mixture was put into a stirring type mixer and mixed for 15 minutes at a product temperature of 30 ° C., then the product temperature was set to 105 ° C., a mechanical impact force was repeatedly applied for 30 minutes, and the carrier was cooled to produce a carrier.

<Production of developer>
418.5 g of the carrier and 31.5 g of each toner were mixed for 20 minutes using a V-type mixer to prepare a developer for a live-action test.

<Evaluation equipment>
Real image evaluation was performed using Konica 9028 (manufactured by Konica) as an image forming apparatus.

"Evaluation methods"
A reflection image (image on paper) and a transmission image (OHP image) are respectively produced on paper and OHP by the above-described evaluation apparatus using a developer using the color toner of the present invention or the comparative color toner. It was evaluated with. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

"saturation"
Using Macbeth Color-Eye 7000, the saturation of the image on the produced paper was measured and compared.

《Light resistance》
The light resistance of the image on the produced paper was evaluated by the same method as in Example 1.

<Hue change>
Using Macbeth Color-Eye 7000, the hue difference between the produced paper and the OHP image was measured and compared.

  The results for the OHP image samples are shown in Table 2.

* 1: C.I. I. PIGMENT RED 122 (HOECHST)
* 2: C.I. I. PIGMENT BLUE 1 (Daiichi Seika Kogyo Co., Ltd.)
As is apparent from Table 2, since the color toner of the present invention exhibits faithful color reproduction and high OHP quality without processing the colorant in advance, the color toner of the present invention is used as a full color toner. Suitable for Furthermore, since the light resistance is good, an image that can be stored for a long time can be provided.

Example 3 (optical recording medium)
<< (a) Production and Evaluation 1 of Optical Recording Medium >>
A recording layer is coated on a polycarbonate substrate with a groove of 5 inches in diameter using the dye (D-3) of the present invention, a reflective layer (Au, thickness 0.10 μm), a protective film (ultraviolet curable resin, thickness 5 μm). ) Were sequentially formed according to a conventional method to produce an optical recording medium 1 of the present invention. For comparison, a comparative optical recording medium 1 was similarly produced using the comparative compound C for the recording layer. When the reflectance was measured, both the optical recording medium 1 of the present invention and the comparative optical recording medium 1 showed 70% or more. Information was recorded on these samples by changing the power with a 633 nm semiconductor laser, and reproduction was performed at 0.8 mW. Further, a similar recording / reproducing experiment was performed after light irradiation for 70 hours at 70,000 lux using a xenon fade meter.

  Table 3 shows the results.

<< (b) Production of optical recording medium and evaluation 2 >>
The optical recording medium 2 of the present invention was prepared in the same manner except that the dye (D-10) of the present invention was added to the coating solution instead of the dye (D-3) of the present invention used in the above examples. Manufactured. Information was recorded on the optical recording medium 2 of the present invention and the comparative optical recording medium 1 by changing the power with a semiconductor laser of 780 nm, and reproduction was performed at 0.8 mW. Further, a similar recording / reproducing experiment was performed after light irradiation for 70 hours at 70,000 lux using a xenon fade meter.

  Table 4 shows the results.

  From Tables 3 and 4, the optical recording media 1 and 2 of the present invention were able to perform good recording 1-reproduction satisfying the DVD standard, and also have stable recording-reproduction characteristics particularly excellent in light resistance. It became clear.

  Similar results were obtained even when other dyes of the present invention (D-17, D-22, D-32) were used instead of the dyes of the present invention described in Tables 3 and 4.

  On the other hand, in the comparative optical recording medium 1, the reflectance was lowered by the reproduction light of the laser, causing the reproduction failure, and the phenomenon that the recording could not be performed even by the light exposure by the xenon fade meter was observed.

Example 4 (color filter)
<Preparation of photosensitive coating agent for color filter>
In order to obtain an RGB color filter, a mosaic pattern was formed on the glass plate by the following method. A photosensitive coating agent for a color filter was prepared using the components shown below. The used photosensitive polyimide resin varnish is a photosensitive polyimide resin varnish containing a photosensitizer.

<Photosensitive coating component for color filter>
<CF-1>
Dye (D-10) of the present invention 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts <CF-2>
Dye (D-14) of the present invention 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts <CF-3>
(Dye D-18 of the present invention) 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts << Preparation of color filter >>
The glass plate treated with the silane coupling agent was set on a spin coater, and the above-described CF-1 color filter photosensitive coating agent was spin-coated at 300 rpm for 5 seconds and then at 2000 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse, and a red mosaic pattern was formed on the glass plate. Similarly, CF-2 and CD-3 were applied and baked according to the above method, and then a black matrix was formed according to a conventional method to obtain a color filter.

  The color filter obtained above has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and also has excellent light transmission properties. Color filter for liquid crystal color display As an excellent property.

Claims (13)

A thermal transfer recording material comprising at least one dye represented by the following general formula (1).
General formula (1)
X = D-B
[Wherein, X represents a group represented by the following general formulas (1-1) to (1-4). D represents a nitrogen atom or ═CR ₁ —, and R ₁ represents a hydrogen atom or a substituent. B represents a group represented by the following general formulas (2-1) to (2-4). However, at least one of X and B has at least one hydrogen bonding group selected from —OH, —NHSO ₂ Rb, —NHCOORb, —NHCONHRb, and —NHCORc, Rb represents a substituent, and Rc represents Represents an aryl group, a heterocyclic group or a branched alkyl group. ]

[Wherein R ₂ , R ₃ or Ra represents a hydrogen atom or a substituent. Z represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a substituent, and the nitrogen-containing heterocyclic ring may form a condensed ring with another ring. ]] 2. The thermal transfer recording material according to claim 1, wherein X in the general formula (1) is represented by the general formula (1-2). The thermal transfer recording material according to claim 1 or 2, wherein B in the general formula (1) is represented by the general formula (2-1). At least one of X and B in the general formula (1) has a hydrogen bonding group, and the hydrogen bonding group is represented by the general formula (1-1) to the general formula (1-4) or the general formula (2-1). The thermal transfer recording according to any one of claims 1 to 3, which is hydrogen-bonded to a nitrogen atom or an oxygen atom on the heterocyclic ring of the group represented by formula (2-4). material. The hydrogen bonding group is —OH or —NHSO ₂ Rb (wherein Rb has the same meaning as Rb in the case of the general formula (1)). The thermal transfer recording material described. A heat-sensitive transfer recording material comprising at least one dye represented by the following general formula (2).

[Wherein R ₂ represents a hydrogen atom or a substituent. D represents a nitrogen atom or ═CR ₁ —, and R ₁ represents a hydrogen atom or a substituent. B represents a group represented by the general formulas (2-1) to (2-4). R ₇ and R ₈ represent a substituent, and R ₉ represents a hydrogen atom or a substituent. ] The thermal transfer recording material according to claim 6, wherein B in the general formula (2) is represented by the general formula (2-1). In the general formula (2), at least one of R ₂ , R ₇ , R ₉ or B is —OH, —NHSO ₂ Rb, —NHCOORb, —NHCONHRb, —NHCORc (where Rb and Rc are represented by the general formula (1)) The thermal transfer recording material according to claim 6 or 7, which has at least one hydrogen-bonding group selected from the group consisting of Rb and Rc in the above case. An image-receiving material is superimposed on a heat-sensitive transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) or (2) on the support, and the heat-sensitive transfer recording material is used as image information. A heat-sensitive transfer recording method, wherein an image is formed on the image-receiving material by heating in response. A heat-sensitive transfer recording material having a dye-donating layer containing at least one dye represented by the general formula (1) or (2) on a support, and a dye image-receiving layer containing a metal ion-containing compound on the support. A thermal transfer recording material, wherein the thermal transfer recording material is heated in accordance with 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. Recording method. A color toner comprising at least one dye represented by the general formula (1) or (2). An optical recording medium comprising at least one dye represented by the general formula (1) or (2). A color filter comprising at least one dye represented by the general formula (1) or (2).