JPH0862836A - Picture forming material and picture forming method - Google Patents

Abstract

PURPOSE: To provide a picture forming material capable of forming a transferred picture good in resolution and without any fogging. CONSTITUTION: This picture forming material is provided with a colorant layer contg. a thermally diffusible coloring matter on a substrate. The thermally diffusible coloring matter has an epoxy group in the molecule, and a polymerization initiator is incorporated in the coloran layer. The initiator is a photopolymerization initiator capable of conducting a polymerization reaction with light. The initiator is also a photo-acid generating agent. A compd. having an epoxy group is incorporated in the colorant layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material, and more particularly to an image forming material having an excellent resolution, and further to a suitable image forming method using the image forming material.

[0002]

2. Description of the Related Art Conventionally, as an image forming method, a recording technology such as an ink jet method, an electrophotographic method, a heat-sensitive transfer method, a heat-sensitive color forming method has been studied. Among them, in the thermal transfer method, by using a thermal diffusible dye as a coloring material, the transfer amount of the dye can be changed according to the change in thermal energy of the thermal head, so that the gradation of the image can be controlled. It is advantageous for full-color recording. However, it was difficult to obtain a high resolution image from the size of one pixel of the thermal head.

In order to improve the above-mentioned resolution, German Patent 2,083,726, US Pat. No. 4,772,581, and Japanese Patent Laid-Open No. 60-25793.
No. 60-34838 and the like, it is proposed to use laser light as a heat source for thermally transferring a heat diffusible dye. According to this image forming method, it is possible to form a higher resolution image by narrowing down the laser light by the optical system. However, according to this method, since it is necessary to thermally diffuse the dye by converting light into heat energy, not only high energy is required as energy to be given, but also an ink layer having a heat diffusible dye and a dye acceptor. Since the adhesiveness to the dye receiving layer provided on the material is likely to vary, the formed image has a drawback that unevenness is likely to occur.

Therefore, JP-A-62-174195 and 63-203382 are used.
JP-A-2004-242242 and the like propose a method of controlling a thermal transfer property of a heat diffusible dye by forming a latent image by radically polymerizing a compound capable of being polymerized by light. According to this method, the energy at the time of latent image formation can be lower than that of the above-mentioned method, and the transfer of the heat diffusible dye onto the dye receiving material can be carried out by devising a device. It has an advantage that a non-existent image can be formed. However, since the thermal diffusion of the dye is involved in the image formation, the degree of polymerization of the polymerizable compound and the polymerization efficiency, due to which the thermal diffusion during the transfer of the thermal diffusion dye in the subsequent step cannot be sufficiently controlled, It was difficult to obtain high resolution images.

Further, in European Patent 0,483,412, a latent image is formed by radically polymerizing a dye imagewise by using a dye-donor material containing a dye having an unsaturated double bond in the molecule as a heat diffusing dye. After forming the image, a method has been proposed in which an image is formed by thermal transfer to a dye image receiving material. According to this method, there is an advantage that latent image formation can be performed by light as in the above method, but since the polymerization of the unsaturated double bond proceeds by radical polymerization, the coloring material layer is produced at the time of production. Oxygen taken in or a certain kind of binder resin may inhibit the polymerization, or the polymerization may be controlled only by the dye.Therefore, the polymerization in the exposed area does not proceed sufficiently, and it is transferred to the exposed area during thermal transfer. The phenomenon may be referred to as image fogging), and it may not be possible to obtain sufficient resolution.

[0006]

The present invention has been made based on the above circumstances. That is, an object of the present invention is to provide an image forming material having a good resolution and having no image fog on a transferred image, and further to provide an image forming method suitable for the image forming material of the present invention.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1. In an image forming material having a color material layer containing a heat diffusible dye on a support, the heat diffusible dye is a dye having an epoxy group in the molecule, and further contains a polymerization initiator in the color material layer. An image forming material characterized by:

2. 2. The image forming material as described in 1 above, wherein the polymerization initiator is a photopolymerization initiator capable of performing a polymerization reaction with light.

3. 3. The image forming material as described in 2 above, wherein the photopolymerization initiator is a photoacid generator.

4. The image forming material as described in 1, 2, or 3 above, wherein the color material layer further contains a compound having an epoxy group.

5. In the image forming method using an image forming material provided with a heat diffusing dye having an epoxy group and a color material layer containing a photopolymerization initiator on a support, the image forming material is imagewise exposed. By changing the thermal diffusivity of the dye by polymerizing the thermal diffusible dye, the surface of the color material layer of the image forming material is brought into close contact with a material capable of receiving the thermal diffusible dye, and then thermocompression bonding. An image forming method characterized by transferring a dye capable of heat diffusion in an unexposed area.

The image forming materials of the present invention and the image forming methods using them will be described in detail below.

(1) Image-forming material and method for producing the same The image-forming material of the present invention is provided with a color material layer containing a heat diffusible dye having an epoxy group in the molecule and a polymerization initiator on a support. It is characterized by that. Examples of the support include paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, resin film or sheet formed by laminating two or more layers of the resin, or wood pulp or cellulose. The film or sheet in which the resin layer is laminated on paper or the like made from pulp, sulfite pulp or the like can be used.

Examples of the resin forming the film or sheet of the above resin include acrylic resins such as acrylic acid esters and methacrylic acid esters, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate and polyacrylate, Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyolefin resins such as polyethylene, polypropylene, polystyrene, polyamide resins such as nylon and aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide , Polyparabanic acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, phenol resin,
Examples thereof include fluororesin and silicone resin. In the present invention, the support made of a resin is preferably stretched into a sheet or film and heat-set from the viewpoint of dimensional stability. The support may have no internal microvoids or may have microvoids. Can be appropriately selected according to the application.

The thickness of the support in the present invention is usually 2 to 50.
It is 0 μm, preferably 4.5 to 200 μm, and is appropriately selected from such a range.

The present invention is characterized by containing a dye having an epoxy group in the molecule as the heat diffusing dye contained in the color material layer.

Specific examples of the dye having an epoxy group in the molecule of the present invention include the following compounds, but the present invention is not limited thereto.

[0019]

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[0020]

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[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

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[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

In addition to the above dyes, dyes or compounds described in JP-A-60-260391 and the like can also be mentioned. The dye of the present invention may be used in combination with a known heat diffusible dye used for image formation depending on the purpose. As the dye, conventionally known naphthoquinone dyes, anthraquinone dyes, azomethine dyes, cyan dyes such as indoaniline dyes, anthraquinone dyes, azo dyes, magenta dyes such as azomethine dyes, methine dyes, azo Examples thereof include yellow dyes such as system dyes, quinophthalone dyes, and anthryothothiazole dyes. The addition amount of the heat diffusible dye is preferably 1 to 80% by weight, more preferably 5 to 70% by weight in the color material layer forming composition.
Further, the amount of the dye having an epoxy group in the molecule of the present invention in the whole heat diffusible dye is usually 50% by weight or more, more preferably 70% by weight.

In the present invention, a polymerization initiator is contained in order to polymerize a dye having an epoxy group in the molecule by the image forming method described later.

The polymerization initiator can be used without particular limitation as long as it is a compound capable of polymerizing an epoxy group by giving a certain energy. The term "polymerization initiator" as used herein means a compound that reacts with an epoxy group immediately after being activated by giving a certain energy, or a compound that produces a compound that directly reacts with an epoxy group by giving a certain energy. Alternatively, it refers to a compound or the like that releases a compound that causes a polymerization reaction of an epoxy group.

As such a polymerization initiator, a compound containing an amino group (for example, an aromatic amine or a modified product thereof, an aliphatic amine or a modified product thereof, an aminopolyamide resin or a modified product thereof), and active hydrogen are contained. Compounds (eg, carboxyl group-containing compounds, sulfonic acid group-containing compounds, mercapto group-containing compounds, etc.), imidazole compounds, organic acid anhydrides, dicyandiamide, etc., but react with epoxy groups directly by adding certain energy. The compound that produces the compound or a compound that releases a compound that causes a polymerization reaction of an epoxy group is preferable, and a photopolymerization initiator that is converted into such a compound in a short time by light energy is more preferable.

As the photopolymerization initiator, a cobalt (III) complex having an amine compound (eg, ethylenediamine, diethylenetriamine, phenylenediamine, etc.) as a ligand and a ligand exchange agent (eg, succinimide, phthalimide, hydantoin, etc.) Examples thereof include compounds that generate an acid upon receipt of the acid (hereinafter referred to as photoacid generators), and among them, photoacid generators capable of causing a chain polymerization reaction of epoxy groups are more preferable.

As such a photo-acid generator, an s-triazine compound substituted with a trihalomethyl group (for example, 2,4,
6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis- (trichloromethyl) -s-triazine, compounds described in JP-A-2-306247, etc., iron arenes Complex (e.g. (η ⁶ -isopropylbenzene) (η ^5-
Cyclopentadienyl) iron hexafluorophosphate, etc.), onium salts (eg, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium trifluoromethanesulfonate, dibutylphenacylsulfonium tetrafluoroborate, dibutyl (4-hydroxyphenyl)) Sulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, tris (4-thiomethoxyphenyl) sulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylseleno N-Hexafluoroantimo Chromatography, tri phenyl tellurocarbonyl hexafluoroantimonate, U.S. Patent 4, 25
No.8,128, J.Polym.Sci., Polym.Chem.Ed.
Polymer Science Polymer Chemical Edition), 17,977 (1979), 18,2677 (1980), 18,2697 (198)
0), Advance in Polym.Sci. (Advance in polymer science), 62,1 (1984), etc.), aryl diazonium salts, diazoketones, o-nitrobenzyl esters, sulfonates, silanol-aluminum Examples thereof include complexes.

When the above-mentioned photo-acid generator is not activated at the wavelength of light energy to be added, it is preferable to perform wavelength sensitization with a photosensitizer. As such a sensitizer, Phenothiazole, phenothiazine, anthracene, perylene, thioxanthone, fluorenone,
Examples thereof include naphthoquinone, anthraquinone, phenanthrenequinone, and the compounds described in Progr. Org. Coatings. (Progress Organic Coatings), 13, 35 (1985) can also be preferably used in the present invention. Further, in order to perform wavelength sensitization from visible light to near infrared, a pyrylium compound, a squarylium compound and the like can be mentioned, and further, European Patent 0,568,993 and US Pat.
The compounds described in 08,811 and 5,227,227 can also be preferably used in the present invention.

The photopolymerization initiators described above may be used alone or in combination of two or more. The addition amount of the photopolymerization initiator and the sensitizer is preferably 0.01 to 20% by weight, and more preferably 0.05 to 10% by weight in the color material layer forming composition. In the present invention, other components that do not inhibit image formation may be added in addition to the polymerization initiator. It is preferable to add a compound having an epoxy group in the molecule to the color material layer of the present invention in order to accelerate and / or control the polymerization of the dye having the epoxy group in the molecule. As the compound having an epoxy group in the molecule, a known crosslinkable epoxy group-containing compound can be used without particular limitation.

Specific compounds include bisphenol A.
Polycondensate of chlorophenol with epichlorohydrin, hydrogenated bisphenol A with epichlorohydrin, polycondensate of brominated bisphenol A with epichlorohydrin, polycondensate with bisphenol F with epichlorohydrin, glycidyl-modified phenol novolac, glycidyl-modified o -Cresol novolac, aliphatic polyglycidyl ether, polyglycol glycidyl ether, monoglycidyl ether, tertiary carboxylic acid monoglycidyl ether, and the like, and further "11290 Chemical Products", Kagaku Kogyo Daily, p.778-p. The compounds described in 787 and the like can also be preferably used in the present invention. Among these, compounds having two or more epoxy groups in the molecule are preferable in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferable. Further, in the present invention, these epoxy group-containing compounds may be used alone or in combination of two or more. Further, the epoxy group-containing compound is usually contained in the coloring material layer forming composition in an amount of preferably 0 to 80% by weight or more, more preferably 0 to 70% by weight or more.

The color material layer of the present invention preferably contains a binder resin for the purpose of providing a film of the color material layer and improving the storage stability of the layer. As the binder resin, a cellulose addition compound, a cellulose ester, a cellulose resin such as a cellulose ether, polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, a polyvinyl acetal resin such as polyvinyl butyral, polystyrene or styrene-acrylonitrile copolymer or the like. Acrylic resin such as styrene resin, poly (meth) acrylic acid ester, poly (meth) acrylic acid, (meth) acrylic acid copolymer, polyvinyl chloride resin such as polyvinyl chloride or vinyl chloride-vinyl acetate copolymer , Polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, rubber-based resins, ionomer resins, olefin-based resins, polyester-based resins, gelatin, casein, and the like. Jill modified products and the like. One of the various binder resins may be used alone, or two or more thereof may be used in combination. The binder resin, in the color material layer forming composition, usually 20 to 99 wt%, more preferably
30 to 95% by weight.

In addition, in order to improve sensitivity, storability of image-forming material, handling property, etc., the colorant layer may further contain a release agent, a plasticizer, a heat-fusible compound, an antioxidant and a filler, if necessary. , Pigments, antistatic agents, etc. may be added. The color material layer may contain a release agent for the purpose of preventing fusion with a material capable of receiving the heat diffusible dye at the time of heat and pressure treatment at the time of image formation described later.

Examples of such a release agent include (modified) silicone oils and (modified) silicone resins, solid waxes such as polyethylene wax, amide wax, Teflon powder, fluorine-based and phosphoric acid ester-based surfactants, and silica. Examples include fillers such as titanium oxide.

As the plasticizer, phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil,
Epoxy stearic acid epoxies, orthophosphoric acid esters, phosphorous acid esters, glycol esters and the like can be mentioned. The heat-meltable compound is a solid at room temperature,
A compound that reversibly becomes a liquid when heated is used.

Examples of the heat-melting compound include terpineol, menthol, 1,4-cyclohexanediol, alcohols such as phenol, amides such as acetamide and benzamide, coumarin, esters such as benzyl cinnamate, diphenyl ether and crown. Ethers such as ethers, camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene,
Single molecular compounds represented by higher fatty acids such as margaric acid, higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, and higher amines such as behenylamine, beeswax, can Delilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and other waxes, ester gum, rosin maleic acid resin, rosin phenol resin and other rosin derivatives, phenol resin, ketone resin , Epoxy resin, diallyl phthalate resin, terpene hydrocarbon resin, cyclopentadiene resin, polyolefin resin,
Polycaprolactone resin, polyethylene glycol,
Examples thereof include polymer compounds represented by polyolefin oxides such as polypropylene glycol. In the present invention, the above-mentioned heat-meltable compound preferably has a melting point or softening point of 10 to 150 ° C.

Examples of the antioxidant include chroman compounds, clamane compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like, and JP-A-59-182785. Issue 60-130735, Issue 61-159644
No. 1, JP-A-1-127387, "Chemical products of 11290" Chemical Industry Daily, compounds described in p.862 ~ 868, etc., and compounds known to improve durability in photographs and other image recording materials. Can be mentioned.

Examples of pigments include carbon black, titanium oxide, iron oxide, phthalocyanine dyes, azo dyes, anthraquinone dyes and azomethine dyes, and examples of fillers include inorganic fine particles and organic resin particles. be able to.

Examples of the above-mentioned inorganic fine particles include silica gel, calcium carbonate, titanium oxide, zinc oxide, barium sulfate, talc, clay, kaolin, acid clay, activated clay, alumina and the like, and the organic fine particles include fluorine resin particles. , Guanamine resin particles, acrylic resin particles,
As resin particles such as silicone resin particles and antistatic agents,
In addition to cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles, etc., `` 11290 chemical products '' Kagaku Kogyo Nikkansha, p.875-p.
The compounds described in 876 and the like can also be preferably used. These additives are preferably contained in the color material layer forming composition in an amount of 0 to 80% by weight, more preferably 0 to 70% by weight. The thickness of the above-mentioned coloring material layer is usually 0.05 to 20 μm, preferably 0.1 to 10 μm.

The color material layer may be a single layer,
Alternatively, if necessary, a multilayer structure having two or more layers having the same composition or different compositions may be provided. The image forming material is not limited to the two-layer structure composed of the support and the color material layer, and other layers may be formed. For example,
For the purpose of preventing fusion with a substance capable of receiving a heat-diffusible dye and blocking (blocking) of the dye, JP-A-59-48188
No., No. 60-224590, No. 61-209195, No. 63-102992,
An overcoat layer may be provided on the surface of the color material layer, as described in JP-A 1-281987, 2-2073, 2-2075, and the like.

Further, for the purpose of improving the adhesiveness with the color material layer on the support, and preventing the transfer and dyeing of the dye to the support side,
JP-A-59-124890, 60-232996, 61-261090,
62-128792, 62-196184, 63-45089, 63-1
It may have an undercoat layer as described in Nos. 35288 and 63-134281. Further, on the back surface of the support, for the purpose of transportability, heat resistance, antistatic, etc., JP-A-60-82387
No. 60, No. 60-94390, No. 60-115486, No. 60-184883, No.
60-219094, 61-279595, 62-251192, 62-28
No. 4784, No. 63-212587, No. 63-214483, No. 64-1586
No. 64-11887, 64-11888, JP 1-214475,
A backing layer as described in JP-A-2-239973 may be provided. The thickness of the overcoat layer, the undercoat layer and the backing layer is usually 0.1 to 1 μm, and the thickness of the oxygen barrier layer is usually 1 to 50 μm. The image forming material is
A coating solution is prepared by dispersing or dissolving the components for forming the color material layer in a solvent, and the coating method is applied to the surface on which the coating solution is laminated and dried, or the layer described above is formed on a peelable sheet. After forming, it can be formed by a transfer method or the like in which only the color material layer is transferred by heating and / or pressing on the surface to be laminated.

As the solvent used in the above coating method, water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene), ketones ( For example, acetone, methyl ethyl ketone), ester solvents (eg ethyl acetate, butyl acetate, etc.), ethers (eg tetrahydrofuran, dioxane), chlorine solvents (eg chloroform, trichloroethylene), amide solvents (eg dimethylformamide, N-methyl). Pyrrolidone), dimethyl sulfoxide and the like. For the coating, conventionally known gravure roll coating method, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted. The layer described above may be formed over the entire surface of the surface to be laminated, or may be formed on a part of the surface, if necessary. Further, other layers can be provided by the same method. In the present invention, when the adhesive strength between the layers to be laminated is insufficient (for example, between the resins to be laminated,
When the difference in wetting angle (contact angle) is large, especially when it is 5 deg or more), it is preferable to treat the surface to be laminated before providing the layer to be laminated. Corona discharge treatment, flame treatment,
Known resin surface modification techniques such as ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, low temperature plasma treatment, and grafting treatment can be applied as they are. Specifically, you can refer to the methods described in "Basics and Applications of Polymer Surfaces (below)", Chemistry Doujin, Chapter 2 and / or "Handbook of Polymer New Materials" Maruzen, Chapter 8, etc. The above can also be used together.

The image-forming material of the present invention is subjected to thermal diffusion of unpolymerized heat-diffusible dye into an acceptable material by the image-forming method described later. In this case, when the above-mentioned image forming material itself is used as an image, there is no particular limitation as long as it is a material that can sufficiently accept the heat diffusible dye, and as a material that can accept such a heat diffusible dye, soft chloride is used. A sheet having a dyeing property itself such as a vinyl sheet may be used, or a dye image receiving material in which an image receiving layer capable of receiving a heat diffusible dye is laminated on a substrate may be used. Examples of the base material of the dye image receiving material described above include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or composite materials obtained by laminating them with paper), vinyl chloride resin sheet, ABS. Resin sheet, polyethylene terephthalate base film, polyethylene terephthalate base film, polyethylene naphthalate base film, polyimide base film, polyetherimide base film, polycarbonate base film, polyether ether ketone base film, polyarylate base film, polysulfone base film, poly It is formed of a single layer such as an ether sulfone base film or various resin films or sheets in which two or more layers are laminated, or various metals such as aluminum or stainless steel. Can be mentioned Irumu or sheet or the like, as these specific ones, JP 59-85972,
60-245593, 61-172795, 61-197282, 62-
87390, 62-158095, 62-198497, 62-278087
No. 63-315293, No. 64-44781, JP-A-1-188392
No. 1, No. 1-280586, No. 2-16051, No. 2-25392, No. 2-11
No. 0457, No. 2-223484, No. 2-225086, No. 2-263689,
The base materials described in JP-A-3-49990, JP-A-3-51187, JP-A-3-76687 and the like can also be preferably used. In addition,
60-30930, JP 61-112693, 62-148293, 62
-152793, 63-1595, 63-231984, 64-44781
No. 64-47536, JP-A Nos. 1-168493, 2-92592, etc., a substrate having a porous structure can also be preferably used in the present invention.

Also represented by resin coated paper for photography,
On the surface or both sides where the image receiving layer of the base film or the base film of the core material is laminated, the neck-in is small, and the drawdown property is good resin, for example, high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene,
Polybutene, polypentene, polystyrene, ethylene-
In the present invention, a polyolefin resin such as vinyl acetate copolymer, a polyester resin such as polyethylene terephthalate, an ionomer resin, nylon, polyurethane or the like may be used alone, or two or more kinds of resins may be hot-melt extrusion laminated. It can be preferably used. These are JP-A 1-263081 and 2-106397.
No. 2,305,688, U.S. Pat.Nos. 4,774,224, 4,999,3
It can be produced by the method described in No. 35, etc.

The base material is preferably one that does not impair the required transparency when transparency is required as in the case of a transparent original such as an OHP or mask material, or a seal application to be stuck to glass or the like. In the case of a reflection image,
White pigments such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay and calcium carbonate are preferably added in order to enhance the sharpness of the formed image. Substrate thickness is usually 10
˜1000 μm, preferably 25 to 800 μm, and is appropriately selected from such a range.

The image-receiving layer is composed of a binder resin and various additives as required. As the binder resin, a known resin that has been conventionally used in the image receiving layer of a thermal transfer recording image receiving sheet can be used, for example, polyester resin, polyvinyl acetal resin, urethane resin, amide resin, cellulose resin, Olefin resin, vinyl chloride resin, acrylic resin, styrene resin, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, and the like, These resins may be used alone or in combination of two or more. The binder resin described above is usually 20 to 99% by weight in the image receiving layer forming composition, and more preferably 50 to 95% by weight.

A peeling agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), a pigment and an antistatic agent may be added to the image receiving layer. Further, a plasticizer, a heat-fusible compound or the like may be added as a sensitizer.

In order to prevent fusion during the formation of an image to be described later, it is preferable to contain a release agent. As such an example, those described in the above-mentioned image forming materials are selected and used at appropriate times. It is usually 0.01 in the image-receiving layer forming composition.
-20% by weight, preferably 0.1-20% by weight.

Examples of the antioxidant include chroman compounds, clamane compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like, and JP-A-59-182785. Issue 60-130735, Issue 61-159644
No. 1, JP-A-1-127387, "Chemical products of 11290", Chemical Daily Co., Ltd., compounds described in p.862 to 868, etc., and compounds known to improve image durability in photographs and other image recording materials. Can be mentioned.

UV absorbers and light stabilizers are disclosed in JP-A-59-158287, JP-A-63-74686, JP-A-63-145089, and JP-A-59-1.
96292, 62-229594, 63-122596, 61-283595
No. 2, JP-A 1-204788, "Chemical products of 11290", Chemical Industry Daily, p.869-875, and the like. As the fluorescent whitening agent, there are JP-A 61-237693, 63-122596, and 63-1.
Examples thereof include compounds described in JP-A-47166, and other compounds known to improve the image durability of other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina and the like, and organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. And so on.

Examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay. As the antistatic agent, a cationic surfactant,
In addition to anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles, etc., "11290 chemical products," Chemical Industry Daily, compounds described in p.875-p.876, etc. It can be preferably used. Examples of plasticizers include phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxy stearic acid and other epoxies, and positive phosphorus. In addition to acid esters, phosphite esters, glycol esters, etc., “11290 chemical products” Kagaku Kogyo Nipposha, p.843-p.85
The compounds described in 7 and the like can also be preferably used.
As the heat-melting compound, the heat-melting compound added to the above-mentioned image forming material can be appropriately selected and used.

The total amount of the additives used in the present invention is usually preferably selected in the range of 0.1 to 30% by weight in the image-receiving layer forming composition. The thickness of the image receiving layer is usually 1 to 30.
m, preferably 2 to 20 μm. The image-receiving layer may be a single layer, or may be provided as a multilayer structure having two or more layers having the same composition or different compositions, if necessary. The image receiving material is
The structure is not limited to the two-layer structure including the base material and the image receiving layer, and other layers may be formed. For example, an intermediate layer (undercoat layer) for the purpose of imparting heat insulating properties, barrier properties, cushioning properties, adhesive properties and the like between the image receiving layer and the base material, and the surface of the image receiving layer with the dye-donating image forming material. For the purpose of preventing fusion of, etc., antistatic on the surface opposite to the overcoat layer and the image receiving layer,
A backing layer may be provided for the purpose of preventing plural sheets from serving, providing slipperiness, preventing adhesion with other image receiving layers, preventing curling, and writing.

When the above intermediate layer, overcoat layer and backing layer are provided, their respective thicknesses are usually 0.
It is preferable to select in the range of 01 to 30 μm. In addition, each of the layers described above may be a single layer, or may be provided as a multilayer structure of two or more layers having the same composition or different compositions as necessary, and the functions may be separated. The image receiving material can be produced by the same method as the above-mentioned image forming material. The image-receiving material may be one formed as described above, or one that is commercially available as a sublimation-type thermal transfer recording image-receiving sheet may be used as it is.

(2) Image forming method In the image forming method of the present invention, a certain amount of energy is applied,
A latent image forming step of polymerizing a dye having an epoxy group with a polymerization initiator, followed by a step of thermally transferring the heat-diffusible dye having an epoxy group of the unpolymerized portion to an acceptable material, in this case, The image forming material itself may be used as an image or an image formed by thermal diffusion dye transfer may be used depending on the application.

The latent image forming step of the present invention, in particular, the imagewise energy corresponding to the image signal applied to the image forming material is not particularly limited as long as it is energy enough to activate the polymerization initiator. The energy can be electromagnetic waves, heat, electricity, ultrasonic waves, and the like.

Among these, in order to obtain a latent image of high resolution in a short time, light energy capable of narrowing down the energy application area to the image forming material containing a photopolymerization initiator, especially ultraviolet light having a wavelength of 1 nm to 1 mm, It is preferable to form a latent image with visible light or infrared light, and as a light source to which such light energy can be applied, for example, a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp. , Quartz mercury lamps, high-pressure mercury lamps and the like. The light energy applied at this time can be appropriately selected and used by adjusting the exposure distance, time and intensity depending on the type of the image forming material.

In the case of collectively exposing the light energy, a mask material having a negative pattern of a desired exposure image formed of a light shielding material may be superposed and exposed. When using an array type light source such as a light emitting diode array, or when controlling the exposure of a halogen lamp, metal halide lamp, tungsten lamp, or other light source with an optical shutter material such as liquid crystal or PLZT, a digital signal corresponding to the image signal is used. It is possible to expose.

In this case, direct writing can be performed without using a mask material. In the case of a laser, it is also possible to appropriately select in accordance with the wavelength range of the photopolymerization initiator or sensitizer contained in the image forming material to be used,
Further, since it is possible to perform scanning exposure according to image data by squeezing light into a beam, it is suitable for direct writing without using a mask material. Further, when a laser is used as a light source, it is easy to narrow the exposure area to a minute size, and high-resolution image formation becomes possible. The laser light source used in the present invention is generally well known, ruby laser, YAG laser, solid-state laser such as glass laser, He-Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He. -Cd laser, N ₂ laser, gas laser such as excimer laser, InGaP laser, AlGaAs laser, GaAsP laser,
InGaAs laser, InAsP laser, CdSnP ₂ laser, GaS
Examples thereof include semiconductor lasers such as b lasers, chemical lasers, and dye lasers.

The exposure direction of the light energy may be from the base material side or the color material layer side as long as the energy is sufficient energy. It is preferable to expose from the direction of less absorption. The latent image formed as described above is
The heat-diffusible dye is transferred by facing the color material layer side of the image forming material and a material capable of receiving the heat-diffusible dye, and applying heat and pressure.

A heat roll, a hot stamp or the like can be appropriately selected and used as the heating and pressurizing means. Further, a heat source used in the heat-sensitive transfer recording method, that is, a thermal head, a laser beam, an infrared flash, a hot pen, and the like can be used in combination with the pressing means.
When a thermal head is used among these heat sources, the shape of the head may be divided for each pixel, or the heating element may be integrated over the entire image or divided into several parts to cover the entire surface. It may be one. The heating temperature, heating time and pressure during the heating and pressurizing treatment vary depending on the heat source, but the heating temperature when using a heat roll is usually 40 to 200 ° C., preferably 60 to 180 ° C., and The transport speed is usually 0.01 to 100 mm / sec, preferably 0.05 to 50 mm / sec. The pressure is usually 0.05 to 10
Kg / cm ^2, preferably from 0.1 to 5 kg / cm ^2. When a hot stamp is used for the heat treatment, the heating temperature is usually in the range of 40 to 200 ° C, preferably 60 to 150 ° C, and the pressure is usually 0.05 to 20 kg / cm ² , preferably 0.5 to 5 kg.
/ Cm ² , and the heating time is usually 0.1 to 20 seconds, preferably 0.
5 to 10 seconds. In the present invention, after forming latent images of a dye having an epoxy group in a plurality of molecules of different tones, the latent images of different tones are sequentially transferred onto the same image-receiving layer to receive an image having a plurality of tones. It can be formed on a layer. In particular, a full-color image can be formed on the image receiving material by sequentially transferring yellow, magenta, cyan or a single color latent image of each color of yellow, magenta, cyan and black onto the same image receiving layer.

Alternatively, the latent image may be once transferred onto a medium such as an intermediate transfer medium and then transferred onto a target image receiving material. In this case, latent images having different color tones may be sequentially formed on the intermediate transfer medium and then collectively transferred to the image receiving material, or may be transferred for each latent image.

[0070]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In the following, "parts" means "parts by weight as active ingredients" unless otherwise specified.

Inventive Examples 1 to 39 and Comparative Examples 1 to 10 were prepared as follows. The constitutions of the image forming materials of the present invention and the comparative examples are shown in Table 1.

<Image forming material> -Support-a) 100 μm stretched transparent polyethylene terephthalate film [T100 manufactured by Diafoyle Hoechst Co., Ltd.] b) 100 μm stretched white polyethylene terephthalate film [W410 manufactured by Diafoyle Hoechst Co., Ltd.] -Surface treatment- a) Corona discharge treatment on the surface b) Ultraviolet treatment by irradiating the surface with ultraviolet rays (low wavelength type: 189 nm) for 10 minutes.

-Undercoat layer-a) A coating solution for forming an undercoat layer having the following composition is applied on a support by wire bar coating and dried to a thickness of 0.1.
A sublayer of μm was formed.

Polyester resin 5.0 parts [Unitika Co., Ltd., Elitel UE3600] Methyl ethyl ketone 45 parts Toluene 40 parts b) The undercoat layer forming coating solution having the following composition is applied on a support by wire bar coating and dried. And then 100
Heat treatment was performed at 30 ° C. for 30 minutes to form an undercoat layer having a thickness of 0.1 μm.

Acrylic resin 20 parts [Mitsubishi Rayon Co., Ltd., Dianarl LR1503] Isocyanate 5 parts [Japan Polyurethane Co., Coronate HX] Butyl acetate 30 parts Toluene 34 parts Xylene 11 parts c) Undercoat layer of the following composition The coating liquid is applied to the support by wire bar coating and dried to a thickness of 0.2 μm.
To form an undercoat layer.

Polyvinyl acetoacetal 10 parts [Sekisui Chemical Co., Ltd., S-REC KW-1] Distilled water 90 parts-Color material layer-1) Color material layer of the present invention a) Color material layer forming coating of the following composition The working solution was applied and dried on the support or the undercoat layer by wire bar coating to form a coloring material layer having a thickness of 0.5 μm.

Polyvinyl acetal resin 8.0 parts [Sekisui Chemical Co., Ltd., S-REC KS-1] Thermal diffusible dye (D-16) 2.0 parts Silicone resin 0.05 parts [Dainichi Seika Chemicals Co., Ltd. SP-2105] Diphenyliodonium hexafluorophosphate 0.01 part Anthracene 0.02 part Methyl ethyl ketone 90 parts b) A color material layer is formed in the same manner as a) except that the heat diffusible dye (D-16) is changed to (D-43). did.

C) The heat diffusible dye (D-16) was added (D-65).
A color material layer was formed in the same manner as in a) except that the above procedure was changed to.

D) A coating material for forming a color material layer having the following composition was applied on a support or an undercoat layer by wire bar coating and dried to form a color material layer having a thickness of 1.0 μm.

Polyvinyl butyral resin 6.0 parts [Sekisui Chemical Co., Ltd., S-REC BX-1] Thermal diffusion dye (D-13) 2.0 parts Alicyclic epoxy resin 2.0 parts [Nippon Ciba Geigy Co., Ltd., Araldite CY] -175] Silicone-based resin 0.05 parts [Dainichi Seika Kogyo KK, Dialomer SP-2105] Triphenylsulfonium hexafluoroantimonate 0.01 parts Phenothiazine 0.02 parts Methyl ethyl ketone 90 parts e) Heat-diffusible dye (D-13) A color material layer was formed in the same manner as in d) except that (D-46) was used.

F) The heat diffusible dye (D-13) was added (D-69).
A color material layer was formed in the same manner as in d) except that the above procedure was changed to.

G) A coating material for forming a color material layer having the following composition was applied on a support or an undercoat layer by wire bar coating and dried to form a color material layer having a thickness of 1.0 μm.

Ethyl cellulose 6.0 parts [Kanto Chemical Co., Inc., 10 cps] 2.0 parts of heat diffusing dye (D-17) Heterocyclic epoxy resin 2.0 parts [Nippon Ciba Geigy Co., Araldite PT810] Silicone resin 0.05 parts [Dainichi Seika Kogyo KK, Dialomer SP-2105] Triphenyltelluronium hexafluoroantimonate 0.01 part Perylene 0.02 part Methyl ethyl ketone 90 parts h) Change the heat diffusible dye (D-17) to (D-47). A color material layer was formed in the same manner as in g) except for the above.

I) The heat diffusible dye (D-17) (D-70)
A color material layer was formed in the same manner as in g) except that the above procedure was changed to.

2) Comparative color material layer j) A color material layer-forming coating solution having the following composition was applied by wire bar coating on a support or an undercoat layer and dried to form a color material layer having a thickness of 1.0 μm. Formed.

Polyvinyl acetal-based resin 8.0 parts [Sekisui Chemical Co., Ltd., S-REC KS-1] Thermal diffusible dye (D-71) 2.0 parts Silicone-based resin 0.05 parts [Dainichi Seika Chemicals Co., Ltd., Dialomer SP-2105] 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2, -bisimidazole 0.01 part Michler's ketone 0.02 part mercaptobenzoxazole 0.01 part methyl ethyl ketone 90 parts k ) A color material layer was formed in the same manner as in j) except that the heat diffusible dye (D-71) was changed to (D-72).

L) A coating material for forming a color material layer having the following composition was applied on a support or an undercoat layer by wire bar coating and dried to form a color material layer having a thickness of 1.0 μm.

Ethyl cellulose 6.0 parts [Kanto Chemical Co., Inc., 10 cps] Thermal diffusion dye (D-73) 2.0 parts Isocyanuric acid EO-modified triacrylate 2.0 parts [Toagosei Co., Ltd., Aronix M-315] Silicone Resin 0.05 parts [Dainichi Seika Kogyo Co., Ltd., Dialomer SP-2105] 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2, -bis Imidazole 0.01 part Michler's ketone 0.02 part Mercaptobenzoxazole 0.01 part Methyl ethyl ketone 90 parts m) A color material was formed in the same manner as in j) except that the heat diffusible dye (D-73) was changed to (D-74).

[0089]

[Table 1]

Comparative heat diffusing dyes (D-71) to (D-74)
The structural formula of is shown below.

[0091]

[Chemical 12]

<Dye image receiving material> a) Sublimation type full color printer S3600 manufactured by Mitsubishi Electric Corporation
-30 type OHP thermal transfer recording image receiving sheet b) Mitsubishi Electric Co., Ltd. sublimation type full color printer S3600
-30-inch thermal transfer recording image-receiving sheet c) 60 μm thick, Beck smoothness 150 seconds on both sides of high-quality paper,
A white polyethylene terephthalate film (W900J, manufactured by Diafoil Hoechst Co., Ltd.) with a thickness of 50 μm is laminated via a urethane adhesive to form a base material, and the image-receiving layer side is subjected to corona discharge treatment to harden gelatin. An aqueous solution with a solid content of 10% containing 5% was applied and dried by wire bar coating to form an intermediate layer with a thickness of 0.1 μm. Next, an image receiving layer forming coating solution having the following composition was applied and dried on the intermediate layer to form an image receiving layer having a thickness of 10.0 μm to form an image receiving material.

Polyvinyl butyral resin 8.0 parts [Denka Butyral # 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd.] Polyether polyol 1.5 parts [Sumitomo Bayern Urethane Co., Ltd. Desmophen 550U] Modified silicone resin 0.5 parts [Shin-Etsu Chemical Co., Ltd. Co., Ltd., X-24-8300] Methyl ethyl ketone 90 parts <Image forming method> a) A printer for bright room sensitive material [Dainippon Screen Co., Ltd.] by applying a wedge pattern to the color material layer side of the image forming material.
Made by P-627-HA] (exposure energy 500mJ
/ Cm ² ) to form a latent image, the color material layer surface is made to face the image receiving layer surface of the image receiving material, and heated and pressed by a heat roll [temperature,
The dye was transferred to the image receiving layer at 155 ° C., the pressure was 2.0 Kg / cm ² , and the feed rate was 10 mm / sec to form an image. The transfer density of the dye image transferred on the dye image-receiving material, the reproduced resolution and the image fog in the exposed area were evaluated according to the following criteria. Table 2 shows the evaluation results and the dye-donor elements and dye-image receiving elements used.

Transfer density: The dye image density [OD] transferred onto the dye image-receiving material is measured by a densitometer [X-rite 31 manufactured by X-rite Co., Ltd.
0TR] ◎ ………… 2.00 ≦ OD ○ ……… 1.50 ≦ OD <2.00 △ ………… 1.00 ≦ OD <1.50 × ……… OD <1.00 Resolution; 150 lines using plate control wedge (manufactured by UGRA) The reproducibility of 2 to 98% of dots / inch is observed with a microscope and the reproduced dot area [Z] is observed. ◎ ………… 2 ≦ Z ≦ 98 [%] ○ ……… 5 ≦ Z ≦ 95 [%] △ ………… 10 ≦ Z ≦ 90 [%] × ………… 15 ≦ Z ≦ 85 [%] Image fog; Dye image density of the exposed area transferred onto the dye image-receiving material is measured with a densitometer ◎ ……… OD ≦ 0.05 ○ ……… 0.05 <OD ≦ 0.10 △ ……… 0.10 <OD ≦ 0.20 × ……… 0.20 <OD

[0095]

[Table 2]

As is clear from Table 2, the examples of the present invention are superior to the comparative examples in terms of resolution and image fog as a whole.

B) A xenon flash lamp [Xenofax FX180 manufactured by Ideal Science Co., Ltd. was used in place of the printer for light-sensitive room light, the exposure time was 1 msec, the exposure energy was 100 mJ / cm ² , and the number of exposures was 5 times. ] Was evaluated in the same manner as in a) except that The transfer density of the dye image transferred onto the dye image receiving material, the reproduced resolution, and the image fog in the exposed area were evaluated according to the same criteria as a). Table 3 shows the evaluation results, and the dye-donor elements and dye-image receiving elements used.

[0098]

[Table 3]

As is clear from Table 3, the examples of the present invention are superior to the comparative examples in terms of resolution and image fog as a whole.

C) Using an argon ion laser [manufactured by American Laser Co., 60 C, output 30 mW, wavelength 514.5 nm, beam diameter 0.65 mm], the diameter was adjusted to 20 μm and the focus was adjusted, and then scanning exposure was performed (scanning pitch 20 μm). To form a latent image,
The color material layer surface is made to face the image receiving layer surface of the image receiving material, and the dye is transferred to the image receiving layer by heat and pressure treatment with a heat roll [temperature, 150 ° C., pressure 4.0 Kg / cm ² , feeding speed; 10 mm / sec]. An image was formed. The reproduced resolution of the dye image transferred on the dye image-receiving material was evaluated according to the following criteria, and the transfer density and the image fog in the exposed area were evaluated according to the same criteria as a). Table 4 shows the evaluation results, and the dye-donor elements and dye-image receiving elements used.

Resolution: Number of resolvable lines per 1 mm when an image is formed with the minimum required average exposure amount [N] ⊙ ∙∙ 25 = N [∘] ∙∙∙ 23 ≦ N <25 [Book] △ ………… 20 ≦ N <23 [Book] × ………… N <20 [Book]

[0102]

[Table 4]

As is clear from Table 4, the examples of the present invention are superior to the comparative examples in terms of resolution and image fog as a whole.

[0104]

INDUSTRIAL APPLICABILITY The image forming material and the image forming method according to the present invention have good resolution and have an effect of preventing image fog on the transferred and formed image.

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Claims (5)

[Claims] 1. An image forming material having a color material layer containing a heat diffusible dye on a support, wherein the heat diffusible dye is a dye having an epoxy group in the molecule, and further in the color material layer. An image-forming material containing a polymerization initiator. 2. The image forming material according to claim 1, wherein the polymerization initiator is a photopolymerization initiator capable of performing a polymerization reaction by light. 3. The image forming material according to claim 2, wherein the photopolymerization initiator is a photoacid generator. 4. The image forming material according to claim 1, wherein the color material layer further contains a compound having an epoxy group. 5. An image forming method using an image forming material comprising a heat diffusing dye having an epoxy group and a color material layer containing a photopolymerization initiator on a support, the image forming material. By subjecting the heat-diffusible dye to polymerization to change the heat-diffusivity of the dye, the surface of the color material layer of the image-forming material is brought into close contact with a material capable of receiving the heat-diffusible dye. The image forming method is characterized in that the dye is exposed to heat and pressure, and the heat-diffusible dye in the unexposed portion is transferred.