JP2864269B2 - Image forming material and method of manufacturing image forming material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an image forming material and a method for producing the image forming material. In particular, the present invention provides an image forming material capable of preventing a transferred image from being stained when an image is transferred to an image receiving layer to obtain a transferred image, and a method for producing the same.

[Background of the Invention]

When an image forming material having a colored photosensitive layer on a support is exposed and developed to obtain an image, and further transferred to obtain a transferred image, a non-image portion is stained with a coloring agent or the like. Dirt may occur.

This is considered to be caused by various causes. For example, when a release layer or a heat softening layer for efficiently transferring a formed image is provided, a color for forming a colored photosensitive layer in these layers is provided. The agent can get in and this can contribute to soiling.

For example, an image forming material having a structure in which a heat softening layer is provided on one surface of a support, and a colored photosensitive layer (may be composed of two layers of a colored layer and a photosensitive layer) is further provided thereon is prepared. When performing, it is common to form a colored photosensitive layer by applying a colored photosensitive layer coating solution containing a pigment on a support with a heat-softening layer, but at that time, in order to remove the solvent of the photosensitive layer,
Generally, a heat drying step is required. However, some pigments, especially organic pigments, are adsorbed on the heat-softening layer by heating.
In some cases, the image is re-transferred onto the surface of a material to be transferred such as paper, which causes soiling.

[Problems to be solved by the invention]

As described above, the conventional image forming material has a problem that the background image may be stained in a finally obtained image.

The present invention seeks to solve this problem,
The purpose of the present invention is to provide a layer of the colored photosensitive layer that easily adsorbs the pigment, for example, when providing a heat-softening layer, or even when using a pigment that is easily adsorbed to such a layer,
The object of the present invention is to obtain an image forming material that can obtain a good image without background smear by preventing the above-described adsorption or the like that causes the background smear, and to prepare such an image forming material. It is an object of the present invention to provide a manufacturing method.

[Means and actions for solving the problems]

The object of the present invention is to provide a colored photosensitive layer on a support, the colored photosensitive layer containing a photoreceptor, a binder, and a pigment, and also performing image exposure and developing to obtain an image. In a colored image forming material for transferring an image to a layer, at least one heat-softening layer and / or release layer is formed between the support and the colored photosensitive layer. This is achieved by an image forming material characterized in that at least the surface of the release layer which is in contact with the colored photosensitive layer has been treated with a silane coupling agent and / or a titanate coupling agent.

Further, in a method for producing a colored image forming material for forming a colored photosensitive layer by applying a colored photosensitive layer coating solution on a support,
The colored photosensitive layer coating solution contains a photoreceptor, a binder, and a pigment, and an intermediate layer coating solution for forming a heat-softening layer or a release layer between the support and the colored photosensitive layer. At least one intermediate layer (thermal softening layer and / or release layer, etc.)
And at least the surface of the intermediate layer which is in contact with the colored photosensitive layer can be achieved by a method for producing an image forming material, which comprises treating with a silane coupling agent and / or a titanate coupling agent.

 The present invention has been achieved with the following background.

That is, it is considered that the background stain is caused by adsorption of the pigment to the heat-softening layer or the like during the heating step. The control of the adsorptivity can be performed by manipulating the surface state of the pigment or by manipulating the surface of the intermediate layer such as the heat-softening layer. As a result, the present inventors have found out that a treatment with a silane coupling agent and / or a titanate coupling agent out of an enormous number of treatment means meets this purpose, and have completed the present invention.

According to the present invention, by processing the intermediate layer as described above, it is possible to obtain a final image free of background stain.

 Hereinafter, the present invention will be described in more detail.

The image forming material of the present invention has a colored photosensitive layer on a support. The colored photosensitive layer contains a photoreceptor, a binder, and a pigment.

The photoreceptor functions as a photosensitive substance, and for example, a diazo compound such as orthoquinonediazide can be used. Other preferable photoconductors that can be used in the present invention will be described later in detail.

The binder is a binder in the photosensitive layer, and various polymer compounds can be used. For example, a preferable binder includes a copolymer of vinyl acetate and vinyl versatate. Other preferable binders that can be used in the present invention will be described later in detail.

The colored photosensitive layer may be configured by forming a photosensitive layer (for example, composed of a photoconductor and a binder) and a colored layer (for example, composed of a pigment and a binder) into two separate layers. In this case, the order of the layers is arbitrary.

In the present invention, the colored photosensitive layer on the support is formed on the support via an intermediate layer such as a thermal softening layer or a release layer. In particular, it is preferable to adopt a structure in which a heat softening layer is formed on a support (furthermore, a release layer is preferably formed thereon), and a colored photosensitive layer is formed thereon. The heat-softening layer will be described later in detail, and can be made of, for example, a vinyl acetate-ethylene copolymer.

It is preferable to form a back coat layer on the surface of the support opposite to the colored photosensitive layer. The back coat layer can be formed of a silicone resin or the like.

The support may be made of any material, for example, preferably one made of polyethylene terephthalate.

Next, the image-forming material of the present invention transfers an image obtained by exposing and developing the image to obtain a transfer image.

Exposure / development can use an appropriate means according to the photoreceptor or the like.

The image forming material of the present invention contains a pigment in the colored photosensitive layer.

In the present invention, a pigment refers to a colorant for forming a colored image.

The pigment as the coloring agent in the colored photosensitive layer may be any of various pigments, and in particular, when used for color proofing, generally requires the usual colors there, namely, yellow, magenta, cyan, and black. A pigment with a matching color tone is required. In addition, metal powder, white pigment, fluorescent pigment, and the like can be used. When the image forming material of the present invention is applied to, for example, a color proof for color image proofing, many pigments known in this technical field can be optionally used as described below.

 (C.I. means color index).

Victoria Pure Blue (CI 42595) Auramine (CI 41000) Katilon Brilliant Flavin (CI Basic 1
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranin OK70: 100 (CI 50240) Erioglaucine X (CI 42080) Fast Black HB (CI 26150) No.1201 Lionol Yellow (CI 21090) Lionol Yellow GRO (CI 21090) Shimura-First Yellow 8GF (CI 21105) Benzidine Yellow 4T-564D (CI 21095) Shimura-Fur Red 4015 (CI 12355) Lionol Red 7B4401 (CI 15830) Fast Gen Blue TGR-L (CI 74160) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50 In the practice of the present invention, the pigment content in the colored photosensitive layer depends on the target optical density and the color sensitivity. It can be determined in consideration of the removability of the layer with respect to the developer. In the present invention, the content of the pigment is preferably 10 to 30% by weight.

Next, the photoreceptor contained in the colored photosensitive layer of the image forming material of the present invention will be described. Various photosensitive materials can be used as the photoreceptor. Such a photoreceptor, for example, undergoes a chemical change in its molecular structure within a short period of time when irradiated with actinic rays, changes its solubility in a solvent, and when a certain solvent is applied. Include all compounds such as monomers, prepolymers, or polymers that can dissolve and remove exposed or unexposed portions.

Examples of photoconductors that can be used include so-called negative / positive types in which revisions such as the exposure part are reduced,
Photocrosslinkable photosensitive resin system represented by esterification of polyvinyl alcohol with cinnamic acid, system in which diazonium salt or its condensate is mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc., or aromatic azide compound Is used as a photo-crosslinking agent, and a system in which a binder such as a cyclized rubber is mixed, and a photosensitive resin utilizing photoradical polymerization or photoion polymerization can also be used.

Further, as a so-called positive-positive type in which the solubility of an exposed portion is increased, for example, a photosensitive composition using o-quinonediazide as a photosensitive agent, specifically, 1,2-
Benzoquinonediazide-4-sulfonyl chloride, 1,
A compound obtained by condensing 2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonylchloride, 1,2-naphthoquinonediazide-6-sulfonylchloride and a compound containing a hydroxyl group and / or an amino group is preferably used. Can be

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, hydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcinol benzaldehyde condensed resin, and pyrogallol acetone condensed resin. Examples of the amino group-containing compound include, for example, aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4-diaminobenzophenone, 4,4-
And diaminodiphenylamine.

Regarding the o-quinonediazide compound, furthermore, J. Ko
“Light Sensitive System” by sar (Wiley & Sons, New
York, 1965) and Matsunaga, Inui, "Photosensitive Polymers" (Kodansha, 1977).

Further, as a positive / positive type, a photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays, a compound having at least one bond decomposable by an acid, and a novolak resin containing two or three different phenols Compositions can also be used.

In the present invention, the content of the photoreceptor in the colored photosensitive layer is, for example, preferably 5 to 80% by weight.

Next, the binder contained in the colored photosensitive layer of the image forming material of the present invention will be described.

As the binder contained in the colored photosensitive layer, any binder can be used as long as it can function as a binder. For example, a polymer compound which is film-forming and solvent-soluble and preferably can be dissolved or swelled in an alkali developing solution Can be used.

Specific examples of such a polymer compound include, for example, a polymer compound containing a structural unit having an aromatic hydroxyl group represented by the following general formula (I) in a molecular structure.

General formula (I) In the general formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or a carboxylic acid group. R ¹³ represents a hydrogen atom, a halogen atom or an alkyl group, and R ¹⁴ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. X represents a divalent organic group linked to a nitrogen atom and an aromatic carbon atom. n is 0 or 1. Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specific examples of the monomer forming the structural unit represented by the general formula (I) include N- (4-hydroxyphenyl)-(meth) acrylamide and N- (2-hydroxyphenyl)-(meth) ) Acrylamide, monomers of (meth) acrylamides such as N- (4-hydroxynaphthyl)-(meth) acrylamide; o-, m- or p-hydroxyphenyl (meth) acrylate monomers; o-, m- or p- And hydroxystyrene monomers. Preferably, o-, m- or p-hydroxyphenyl (meth) acrylate monomer, N-
(4-Hydroxyphenyl)-(meth) acrylamide monomer, and more preferably N- (4-hydroxyphenyl)-(meth) acrylamide monomer.

In the present invention, it is preferable to use a copolymer of a monomer forming the structure represented by the general formula (I) and the following monomers and the like as the binder.

In each of the above formulas, R ¹⁵ represents a hydrogen atom, an alkyl group, or a halogen atom, and R ¹⁶ represents an alkyl group, a phenyl group, or a naphthyl group.

When the above copolymer is used, the proportion of the group having an aromatic hydroxyl group represented by the general formula (I) in the copolymer is preferably from 1 to 30 mol%.

The proportion of units formed from the acrylonitriles in the copolymer is preferably from 0 to 50 mol%, and more preferably from 5 to 40 mol% in view of developability. The proportion of the structural unit formed from the alkyl acrylates is preferably from 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and more preferably from 60 to 95 mol%.
~ 95 mol% gives the most suitable developability.

In addition to the structural units described above, the above-mentioned acrylic acid such as acrylic acid or methacrylic acid may be copolymerized with the polymer compound as the structural unit for the purpose of finely adjusting the developability. In that case, the proportion of the acrylic acid in the polymer compound in the copolymer is preferably 0 to 20 mol% in consideration of the development latitude.
Most preferably, it is 1010 mol%.

The weight average molecular weight of such a polymer compound is preferably from 1,000 to 100,000 from the viewpoint of developability when using a low alkaline aqueous solution as a developer, or resolution,
Further, those having a range of 1,000 to 30,000 are preferable. These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such a polymer compound include a copolymer having the following structure.

(Weight average molecular weight: 1,000 to 30,000) l: m: n = (1 to 25) :( 5 to 40) :( 50 to 95) In the image forming material of the present invention, as a binder constituting the colored photosensitive layer A polymer compound having a carboxylic acid vinyl ester polymerization unit represented by the following general formula in the molecular structure can also be preferably used.

RCOOCH = CH ₂ where R represents an alkyl group having 1 to 17 carbon atoms.

Any polymer compound having the structure as described above can be used arbitrarily, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit represented by the above general formula, the following examples are preferable. The name and chemical formula are shown together.

Vinyl CH ₃ COOCH = CH ₂ vinyl propionate vinyl CH ₃ CH ₂ COOCH = CH ₂ butyric acid _{CH 3 (CH 2) 2 COOCH} = CH 2 vinyl pivalate _{(CH 3) 3 CCOOCH = CH} 2 caproic acid vinyl CH ₃ ( CH ₂ ) ₄ COOCH = CH ₂ Vinyl caprylate CH ₃ (CH ₂ ) ₆ COOCH = CH ₂ Vinyl caprate CH ₃ (CH ₂ ) ₈ COOCH = CH ₂ Vinyl laurate CH ₃ (CH ₂ ) ₁₀ COOCH = CH ₂ Vinyl myristate CH ₃ (CH ₂ ) ₁₂ COOCH = CH ₂ Vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COOCH = CH ₂ Vinyl stearate CH ₃ (CH ₂ ) ₁₆ COOCH = CH ₂ Vinyl versatate (R ¹ and R ² are alkyl groups, and the total number of carbon atoms is 7.
That is, the form of the _{^{R 1 + R 2 = C 7}} H 16) The carboxylic acid vinyl ester monomer, the number of carbon atoms constituting the main chain of the carboxylic acid is more preferably from 1 to 4. Particularly, vinyl acetate is preferred.

The above R also includes an alkyl group having a substituent, that is, it is included in a vinyl ester polymerization unit of a substituted carboxylic acid.

The polymer compound may be a polymer obtained by polymerizing one kind of vinyl carboxylate, a polymer obtained by copolymerizing two or more kinds of vinyl carboxylate, or a polymer that can be copolymerized with vinyl carboxylate. The copolymer may be a copolymer having an arbitrary component ratio with the monomer.

Examples of the monomer unit that can be used in combination with the polymerization unit represented by the general formula include ethylene-based unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene, Styrenes such as -methylstyrene and p-chlorostyrene; for example, acrylic acids such as acrylic acid and methacrylic acid; for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; for example, diethyl maleate and maleic acid Dibutyl, di-2-ethylhexyl maleate, dibutyl fumarate,
Diesters of unsaturated dicarboxylic acids such as di-2-ethylhexyl fumarate, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methylene aliphatic monocarboxylic acid esters such as α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, etc., for example, nitriles such as acrylonitrile, methacrylonitrile, amides such as acrylamide, for example, acrylanilide, p- Anilides such as chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide; for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether; Nyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1 Ethylene derivatives such as -nitroethylene, for example, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene,
-Vinyl monomers such as N-vinyl compounds such as vinylpyrrolidone. These vinyl monomers generally have a structure in which an unsaturated double bond is cleaved and are present in a polymer compound.

When the polymer compound represented by the above general formula is used in the present invention, a compound having a vinyl acetate polymerized unit in the molecular structure is particularly preferred. Among them, those having 40 to 95% by weight of vinyl acetate polymerized units, those having a number average molecular weight (MN) of 1,000 to 100,000, and those having a weight average molecular weight (MN)
Those having a W) of 5,000 to 500,000 are preferred.

More preferably, vinyl acetate polymerized units (especially when this is 40
~ 95 wt%) and a polymer compound having a carboxylic acid vinyl ester polymerized unit longer than vinyl acetate,
Particularly, those having a number average molecular weight (MN) of 2,000 to 60,000 and a weight average molecular weight (MW) of 10,000 to 150,000 are preferable.

In this case, as a monomer constituting a polymer compound having a vinyl acetate polymerized unit by copolymerizing with vinyl acetate,
Any monomer can be used as long as it can form a copolymer, and for example, it can be arbitrarily selected from the monomers exemplified above.

Hereinafter, copolymers that can be used as the polymer compound in the present invention are listed by showing their monomer components. However, as a matter of course, the present invention is not limited to the following example.

Vinyl acetate-acrylic ester Vinyl acetate-maleic acid ester Vinyl acetate-ethene Vinyl acetate-vinyl carboxylate Vinyl acetate-styrene Vinyl acetate-crotonic acid Vinyl acetate-maleic acid Vinyl acetate-2-ethylhexyl acrylate Vinyl acetate-di-2 -Ethylhexyl maleate vinyl acetate-methyl vinyl ether vinyl acetate-vinyl chloride vinyl acetate-N-vinyl pyrrolidone vinyl acetate-vinyl propionate vinyl acetate-vinyl pivalate vinyl acetate-vinyl versatate vinyl acetate-vinyl laurate vinyl acetate-stearic acid Vinyl vinyl acetate-vinyl versatate-ethylene vinyl acetate-vinyl versatate-2-ethylhexyl acrylate vinyl acetate-vinyl versatate-vinyl laurate Vinyl acetate-vinyl versatate-crotonic acid vinyl propionate-vinyl versatate vinyl propionate-vinyl versatate-crotonic acid pivalic acid-vinyl stearate-maleic acid In the present invention, a novolak resin is used as a binder. You can also.

The novolak resin is generally obtained by polycondensation of at least one phenol and an active carbonyl compound, and any of such novolak resins can be used.

The phenols include all compounds in which at least one of the hydrogen atoms bonded to the aromatic ring is substituted with a hydroxyl group. Specific examples of such phenols include phenol, o-cresol, m-cresol, p
-Cresol, 3,5-xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol,
Catechol, resorcin, hydroquinone, pyrogallol, phloroglucin, alkyl group (1 to 8 carbon atoms)
And substituted phenols.

The active carbonyl compound includes, for example, aldehyde,
Ketones and the like are included, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Examples of the novolak resin include phenol formaldehyde novolak resin, m-cresol formaldehyde novolak resin, phenol / m-cresol / formaldehyde copolycondensate resin, phenol / p-cresol / formaldehyde copolycondensate resin, and m-cresol / p- Cresol / formaldehyde copolycondensate resin, o-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / o-cresol / m-
Cresol / formaldehyde copolycondensate resin, phenol / o-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / m-cresol / p
-Cresol-formaldehyde copolycondensate resin and the like.

Preferred novolak resins are phenol formaldehyde novolak resins, having a weight average molecular weight MW of 3500-50.
0, those having a number average molecular weight MN in the range of 1,000 to 200 are preferred.

The measurement of the molecular weight of the polymer compound in the present specification including the molecular weight of the novolak resin is performed by GPC (gel permeation chromatography). The calculation of the number average molecular weight MN and the weight average molecular weight MW are described in Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan”, pages 800-805.
According to the method described on page (1972), the method is carried out by a method of leveling the peak of the oligomer region (connecting the center of the peak and the center of the valley).

In the novolak resin, pyrolysis gas chromatography (PGC) is used as a method for confirming the quantitative ratio of different phenols used in the synthesis.
The principle of pyrolysis gas chromatography
Apparatus and experimental conditions are described, for example, in the Chemical Society of Japan, Tsuge "Core Experiment Chemistry Course" Vol. 19, Polymer Chemistry [I] pp. 474-4
The qualitative analysis of novolak resin by pyrolysis gas chromatography is described in Morio Tsuge, Takashi Tanaka, and Masayuki Tanaka, “Analytical Chemistry,” p. 85 (issued in Maruzen 1978).
Volume 18, pages 47 to 52 (1969).

In the present invention, the colored photosensitive layer includes a novolak resin (referred to as component (b)) and a polymer compound having a carboxylic acid vinyl ester polymerized unit represented by the above general formula in the molecular structure (referred to as component (c)). Is preferably contained in a weight ratio range of (b) / (c) = 5/95 to 80/20. This range is preferred in terms of color reproducibility, deformation due to heat (dimension deviation), and resistance to discoloration. A particularly preferred ratio of the components (b) and (c) is in the range of (b) / (c) = 10/90 to 60/40 by weight.

Further, in the present invention, other polymer compounds that can be used as a binder for the colored photosensitive layer include sulfoalkyl esters of (meth) acrylic acid (co) polymer, vinyl acetal (co) polymer, and vinyl ether (co). ) Polymers, acrylamide (co) polymers, styrene (co) polymers, cellulose derivatives and the like.

The thickness of the colored photosensitive layer in the image forming material of the present invention,
It can be appropriately determined according to the target optical density, the type of the coloring agent used in the colored photosensitive layer, the content thereof, and the like.
Within the allowable range, the smaller the thickness of the colored photosensitive layer is, the higher the resolution becomes, and the better the image quality is. Thus, the membrane thickness is preferably usually being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In the method for producing an image forming material of the present invention, the colored photosensitive layer can be generally formed by applying a colored photosensitive layer coating solution containing a photoreceptor, a binder, and a pigment on a support.

Here, an organic solvent can be used as a solvent for forming the coating liquid. In carrying out the present invention, any organic solvent that can be used as a coating solution for the colored photosensitive layer is optional, and for example, all known various organic solvents can be used.

Examples of the organic solvent that can be used include, for example, n-
Hexane, cyclohexane, n-pentane, benzene,
Hydrocarbons such as toruene and xylene, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-
Propyl alcohol, t-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, n-butyl alcohol, 1-pentanol, 2-pentanol, 1-
Alcohols such as hexanol, ketones such as acetone, cyclohexane, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone and methyl isobutyl ketone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether and the like Diethylene glycols, other methyl lactate, ethyl lactate, methyl propionate, methyl butyrate,
Examples include esters such as ethyl acetate, nitriles such as acetonitrile and propionitrile, 1,4-dioxane, dimethylformamide, dimethylsulfoxide, methylene chloride, chloroform, and carbon tetrachloride. Of these, aromatic hydrocarbons such as benzene, toluene and xylene, ketones and esters are preferred, and cyclohexanone, toluene and methyl lactate are particularly preferred.

In the practice of the present invention, a plasticity and coatability improver may be further added to the colored photosensitive layer, if necessary.

Examples of the plasticizer include various low molecular compounds such as phthalates, triphenyl phosphates and maleates, and examples of the coating improver include surfactants such as a fluorine-based surfactant and ethyl cellulose polyalkylene ether. Nonionic activators and the like.

When constituting the image forming material of the present invention, the colored photosensitive layer can be divided into two layers, a colored layer composed of a coloring agent and a binder, and a photosensitive layer composed of a photosensitive composition. In this case, either layer may be arranged on the support side.

The colored image forming material of the present invention can be embodied as a color proof.

In this case, the colored photosensitive layer of the colored image forming material is removed imagewise by development following imagewise exposure to form a colored image.

The support used to construct the image forming material of the present invention is optional, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film, is preferable in terms of dimensional stability against water and heat. In addition, an acetate film, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyethylene film and the like can be used.

The image forming material can be used in the form of transferring an image to a material to be transferred.

In the present invention, at least one intermediate layer is formed between the support and the colored photosensitive layer. In such a case, the image is efficiently transferred onto the material to be transferred, and the support after the image transfer is performed. In order to facilitate the peeling of the body, an intermediate such as a release layer (including a release-treated surface of the support) between the support and the colored photosensitive layer or a heat-softening layer is used as the intermediate. Provide a layer.

The release layer is, for example, a silicone resin, a fluororesin, polyethylene, a polypropylene ethylene-α-olefin copolymer, a propylene-α-olefin copolymer, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, It can be formed from an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, an ionomer resin, a wax, a polyamide resin such as nylon or copolymerized nylon.

Further, a silicon resin or a fluorine resin may be added to a melamine resin or a polyacrylate urethane resin to be used.

Further, since a polypropylene film, a polyethylene film, and the like show a good release property without performing a special release treatment, the release layer is preferably provided with a polypropylene layer or a polyethylene layer, which is thinner than the thickness of the support. It can be.

The method of providing a polypropylene layer or a polyethylene layer on a support is as follows: (1) A solution obtained by dissolving polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, or the like in an organic solvent is used as an adhesive. A so-called dry lamination method in which these adhesives are applied to a support, dried by hot air or heating, and then a polypropylene film or a polyethylene film is laminated and pressed and laminated under heating; (2) ethylene And vinyl acetate copolymer, ethylene and acrylate copolymer, polyamide resin, petroleum resin, rosins, waxes or mixtures thereof as adhesives, and heat these adhesives as they are to keep them in a molten state While on the support, doctor blade method, roll coating method, gravure method, Later applied in Bath roll method or the like,
A so-called hot-melt laminating method in which a polypropylene film or a polyethylene film is immediately laminated and then heated and cooled as necessary, followed by cooling, so-called hot melt laminating method; A so-called extrusion lamination method in which the support is pressed and laminated while the film is in a molten state; (4) a plurality of extruders are used when forming a film to be a support by a melt extrusion method Using, with polypropylene in a molten state, or polyethylene, by a single formation,
A so-called co-extrusion method or the like in which a polypropylene layer or a polyethylene layer is formed on a support film can be used.

The thickness of the release layer is suitably in the range of 0.01 to 30 μm, particularly preferably in the range of 0.1 to 5 μm.

 Next, the heat softening layer will be described.

The thermal softening layer has the property of softening at the temperature during thermal transfer, and can be formed of a thermoplastic resin.
As the thermoplastic resin, those having a softening point of -30 ° C to 150 ° C are preferable. The softening point temperature mentioned here is a value indicated by the VICAT softening point or the ring and ball method. In the present invention, the following can be specifically mentioned as preferred resins.

Polyolefins such as polyethylene and polypropylene.

Ethylene copolymers such as ethylene and vinyl acetate, ethylene and acrylate, and ethylene and acrylic acid.

 PVC.

 Vinyl chloride copolymers such as vinyl chloride and vinyl acetate.

 Polyvinylidene chloride.

 Vinylidene chloride copolymer.

 polystyrene.

 Styrene and styrene copolymers such as maleic anhydride.

 Polyacrylate.

 Polyester resin.

 Porethane resin.

Acrylate and acrylate copolymers such as vinyl acetate.

 Polymethacrylate.

Methacrylate copolymers such as methyl methacrylate and vinyl acetate, and methyl methacrylate and acrylic acid.

 Polyvinyl acetate.

 Vinyl acetate copolymer.

 Vinyl butyral resin.

Polyamide resins such as nylon, copolymerized nylon and N-alkoxymethylated nylon.

 Synthetic rubber.

 Petroleum resin.

 Chloride rubber.

 Polyethylene glycol.

 Polyvinyl alcohol hydrozine phthalate.

Cellulose derivatives, cellulose acetate phthalate, cellulose acetate succinate.

 Shellac.

 wax.

The heat softening layer can be provided on the support using a known method.

The thickness of the heat-softening layer is suitably in the range of 1 to 50 µm, particularly preferably in the range of 5 to 30 µm.

As a method of providing the release layer on the heat-softening layer, a method in which a solution in which the release layer resin is dissolved in an organic solvent, or a method in which an emulsified solution is applied on the heat-softening layer, a polypropylene film, or a polyethylene film Is laminated on the thermal softening layer.

In the present invention, at least the surface of the intermediate layer, particularly the heat-softening layer, which is in contact with the colored photosensitive layer, is treated with a silane coupling agent and / or a titanate coupling agent.

In the present invention, various known silane coupling agents can be used, and specifically, TSL8
308 (vinyltrichlorosilane), TSL8311 (vinyltriethoxysilane), TSL8320 (γ-chloropropyltrimethoxysilane), TSL8395 (γ-chloropropylmethyldichlorosilane), TSL8325 (γ-chloropropylmethyldimethoxysilane), TSL8326 ( γ-chloropropylmethyldiethoxysilane), TSL8331 (γ-aminopropyltriethoxysilane), TSL8340 (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane), TSL8345 (N- (β-aminoethyl ) -Γ-aminopropylmethyldimethoxysilane), TSL8380 (γ-
Mercaptopropyltrimethoxysilane), TSL8350
(Γ-glycidoxypropyltrimethoxysilane), TS
L8355 (γ-glycidoxypropylmethyldimethoxysilane), TSL8370 (γ-methacryloxypropyltrimethoxysilane), TSL8375 (γ-methacryloxypropylmethyldimethoxysilane, all manufactured by Toshiba Silicon Corporation) and the like can be used.

In the present invention, as the titanate coupling agent, various known ones can be used. Specifically, A-1 (tetra-i-propoxytitanium), B-1
(Tetra-n-butoxytitanium), TOT (tetrakis (2-ethylhexyloxy) titanium), TST (tetrastearyloxytitanium), TAA (di-i-propoxybis (acetylacetonato) titanium), TAT (di-n −
Butoxybis (triethanolaminato) titanium), TL
A (dihydroxybis (lactato) titanium), TOG (titanium-i-propoxyoctylene glycolate), TT
S (titanium stearate, manufactured by Nippon Soda Co., Ltd.), EL
-105 (alkyl titanate, manufactured by Toyo Morton Co., Ltd.), K
R TTS (isopropyl triisostearoyl titanate), KR 38S (isopropyl tris (dioctyl pyrophosphate) titanate), KR 44 (isopropyl tri (N-aminoethyl-aminoethyl) titanate), KR 46B (tetraoctyl bis (ditridecyl phos) Phyto) titanate), KR 55 (tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate), KR 138S (bis (dioctyl pyrophosphate) oxyacetate titanate), KR 238S (bis (bis (dioctyl pyrophosphate) oxyacetate titanate) Dioctyl pyrophosphate) ethylene titanate), KR 2S (isopropyltrioctanoyl titanate), KR 7 (isopropyl dimethacrylisostearoyl titanate), KR 9S (isopropyl tridodecylbenzenesulfonyl titanate), KR 11 ( Sopropylisostearoyl diacryl titanate), KR 12 (isopropyl tri (dioctyl phosphate) titanate), KR 34S (isopropyl tricumyl phenyl titanate), KR 41B (tetraisopropyl bis (dioctyl phosphite) titanate, manufactured by Ajinomoto Co., etc.) Can be used. Especially A
-1, B-1 can be preferably used.

The coupling agent can be treated by dissolving the coupling agent in an organic solvent to form a thin solution (for example, a dilute solution of about 1% by weight), and applying this to the surface to be processed, such as the middle of the layer to be processed.

Here, as the solvent for dissolving the coupling agent, any solvent can be used as long as it dissolves the coupling agent to be used, and various solvents can be used. Examples thereof include hydrocarbons such as n-hexane, cyclohexane, n-pentane, benzene, toluene, xylene, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol,
sec-butyl alcohol, isobutyl alcohol, n-
Alcohols such as butyl alcohol, 1-pentanol, 2-pentanol and 1-hexanol, acetone, cyclohexane, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-
Ketones such as butyl ketone and methyl isobutyl ketone,
Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, etc.
Examples thereof include 1,4-dioxane, dimethylformamide, dimethylsulfoxide, methylene chloride, chloroform, and carbon tetrachloride. Of these, aromatic hydrocarbons and ketones such as benzene, toluene and casylene, and alcohols such as n-butanol are particularly preferable, and cyclohexanone,
Toluene and n-butanol.

The image forming material of the present invention forms an image portion by exposing and developing the image portion, and transfers at least the formed image portion to a material to be transferred to obtain a transfer image.

For example, when embodied as a multicolor image forming method, the basic method can be roughly classified into the following methods (I) and (II).

(I) A first colored image forming material having a first color image forming layer on a support is superimposed on a material to be transferred, at least the colored image forming layer is transferred to the material to be transferred, and the support is peeled off. I do. Next, image exposure is performed through a first-color film original corresponding to the first color, followed by development processing to form a first-color image on the transfer-receiving material.

Next, at least the colored image forming layer of the second colored image forming material having the second color image forming layer having a different color tone from the first color is transferred onto the first color colored image layer on the transfer-receiving material. After the registration image of the second color film original corresponding to the second color (what is generally called a registration mark image is used) is registered with the first color registration mark image, the second color image is registered. Image exposure is performed through a film original, followed by development processing to obtain a two-color matched image on the material to be transferred. Similarly, the same processing is performed on the third and fourth colors to obtain a multicolor image.

This method is described in JP-B-47-27441 and JP-B-56-5
This is known from, for example, JP-A-01217.

(II) A first color image is formed on the first color image forming material, and at least the colored image is transferred to a material to be transferred, and the support is peeled off. Further, after forming the second color colored image on the second color colored image forming material, the second color registered image formed thereby is registered with the first color registered image on the material to be transferred. Then, the second-color image is transferred onto the first-color image, and the support is peeled off to obtain a two-color image. Similarly, the colored images of the third color and the fourth color are transferred onto the transfer material to obtain a multicolor image. In some cases, the multicolor image is indirectly transferred onto another material to be transferred,
Sometimes a multi-thread image is obtained.

This type of method is disclosed in JP-A-47-41830 and JP-A-59-9.
Nos. 7140, 60-23649 and U.S. Pat. No. 3,775,113.

The image forming material is usually imagewise exposed through a color separation mask or the like and then developed to form an image. At this time, it is possible to adopt a mode in which only the image portion is directly transferred and laminated on the material to be transferred from the image obtained on the support. That is, it is one preferable embodiment that substantially only the colored image layer that forms an image is transferred and laminated.

In this case, the transfer to the surface to be transferred is performed efficiently, and in order to facilitate peeling of the support after image transfer, the surface of the support is subjected to a release treatment with an appropriate oil-repellent substance as described above, Alternatively, it is preferable to provide a release layer on the support.

The image-forming material of the present invention can be exposed to light suitable for the colored photosensitive layer, in particular for the photoreceptor, and then developed to obtain an image. The developer used for developing the image forming material can be arbitrarily used as long as it has a developing effect of developing the material to be processed.
Preferably, a developer containing an alkali agent and an anionic surfactant is used.

Examples of usable alkali agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium phosphate dibasic or tribasic, sodium metasilicate, sodium carbonate, ammonia (2) mono, di, or trimethylamine, mono, di, etc.
Or organic amine compounds such as triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, and the like.

Examples of anionic surfactants that can be used include: (1) higher alcohol sulfates (eg, sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, secondary sodium alkyl sulfate, etc.) (2) aliphatic alcohol phosphate ester salts (for example,
(3) Alkyl aryl sulfonates (for example, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium sodium metanitrobenzenesulfonate, etc.) (4) Alkyl amide sulfonates (5) Sulfonates of dibasic aliphatic esters (eg, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.) (6) Formaldehyde condensate of alkyl naphthalene sulfonate (eg, formaldehyde condensation of sodium dibutyl naphthalene sulfonate) Thing etc.).

The alkali agent and the anionic surfactant can be used in any combination.

〔Example〕

 Hereinafter, examples of the present invention and comparative examples will be described.

Needless to say, the present invention is not limited to the embodiments described below, but can take various forms.

Example 1 In order to obtain an image forming material of the present invention, a coating solution for treating an intermediate layer (here, a heat-softening layer) of a support was prepared as a titanate coupling agent, tetra-i-propoxytitanium (trade name: A- 1, Nippon Soda Co., Ltd.) 1% by weight n-
A butanol solution was prepared. For the formation of a color image, four colored photosensitive layer dispersions having the following formulation were prepared.

Colored photosensitive layer dispersion (cyan) 1,2-naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Cyanine blue 4920 (manufactured by Dainichi Seika) 1.10 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (magenta) 1,2-Naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Seika Fast Carmine 1483 (Dainichi Seika) 1.10 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (yellow) 1,2-naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Seika First Yellow H-7505 (manufactured by Dainichi Seika) 1.10 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (black) 1,2-naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.19 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 14.21 g Carbon black MA-100 (manufactured by Mitsubishi Kasei) 1.85 g Cyclohexanone 72.05 g Also, the following support was separately prepared.

That is, on a polyethylene terephthalate film, an ethylene-vinyl acetate copolymer (trade name: Evaflex, manufactured by Mitsui DuPont Chemical Co., Ltd.) is applied by extrusion lamination to a thickness of 30 μm, thereby having a heat-softening layer. A support was made.

The thus obtained support having a heat-softening layer was treated by applying the titanate coupling agent coating solution obtained above. The above four colored photosensitive layer dispersions were further applied thereon so as to have a dry film thickness of 1 μm, and then dried.

Thus, four colored image forming materials were prepared.

The color separation screen positive films of the respective colors were superimposed on the polyethylene terephthalate film surfaces of the four colored image forming materials obtained as described above, and 5
Perform image exposure for 20 seconds from a distance of 0 cm.
By immersing for 2 seconds, development was performed to form four colored images.

Close contact with the image surface of the <Developer> Na ₂ CO ₃ 15g surfactant (Kao Atlas Co., Ltd. PELEX NBL) 50 g Distilled water 100g then the yellow image and the art paper,
After passing through a pair of nip rolls heated to 80 ° C. under a pressure of 5 kg / cm ² at a speed of 50 cm / min, the support was peeled off. Peeling was easily performed, and only the yellow image portion was transferred onto the art paper.

Subsequently, a colored image was transferred in the order of magenta, cyan, and black, thereby obtaining a color proofing image of four colors on art paper.

The color proofing image obtained by the present embodiment is capable of obtaining a transfer image with less color fogging (ground stain) in a non-image portion, and the transfer image is very similar to an actual printed matter. there were.

Example 2 1% by weight n-butanol solution of tetra-n-butoxytitanium (trade name: B-1, manufactured by Nippon Soda Co., Ltd.) which is a titanium coupling agent solution as a coating solution for treating an intermediate layer of a support. Was prepared. In the same manner as in Example 1, the support with the heat-softening layer was treated with this coating solution, and after the colored photosensitive layer was applied, exposure and development transfer were performed to obtain a color proofing image composed of four colors. .

The color proofing image obtained in this example was able to obtain a transfer image with no background smear and excellent image quality, and was very similar to an actual printed matter.

Example 3 TSL8311 containing vinyltriethoxysilane as a silane coupling agent solution was used as a coating solution for treating an intermediate layer of a support, and the other steps were carried out in the same manner as in Example 2. Thereby, the same effect as that of the second embodiment was obtained.

Comparative Example A colored photosensitive layer dispersion having the following composition was prepared.

Colored photosensitive layer dispersion (cyan) 1,2-naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Cyanine blue 4920 (manufactured by Dainichi Seika) 1.1 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (magenta) 1,2-Naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Seika Fast Carmine 1483 (Dainichi Seika) 1.1 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (yellow) 1,2-Naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.37 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 15.36 g Seika First Yellow H-7555 (manufactured by Dainichi Seika) 1.1 g Cyclohexanone 71.47 g Colored photosensitive layer dispersion (black) 1,2-naphthoquinonediazide-4-sulfonic acid-p-
Cresol formalin ester polymer 2.19 g vinyl acetate-vinyl versatate (80:20 parts by weight)
Copolymer (49.7% methanol solution) 14.21 g Carbon black MA-100 (manufactured by Mitsubishi Kasei) 1.85 g Cyclohexanone 72.05 g The dispersion of the colored photosensitive layer obtained here was applied to the heat-softening layer used in Examples 1 and 2. It was coated on a support having a dry film thickness of 1 μm and then dried to prepare four colored image forming materials.

The four colored image forming materials obtained as described above were exposed and developed in the same manner as in Example 2, and transferred to art paper to obtain a color proofing image composed of four colors on art paper. .

The color proofing image obtained by this method had a background stain on the non-image portion, and was inferior in color image quality.

〔The invention's effect〕

As described above, the image forming material of the present invention has an effect that, even when an intermediate layer such as a thermal softening layer is provided, it is possible to obtain a good image without background contamination,
The method for producing an image forming material of the present invention can provide such an advantageous image forming material.

──────────────────────────────────────────────────の Continuing on the front page (72) Kunio Shimizu, Inventor Kunio, Sakura-cho, Hino-shi, Tokyo Konica Corporation (72) Inventor Toyoyoshi Urano 1000, Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Prefecture Mitsubishi Chemical Corporation Inside the research institute (72) Inventor Tetsuya Masuda 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Inside the Mitsubishi Chemical Research Institute (56) References JP-A 1-179038 (JP, A) JP-A 63-208038 (JP) JP-A-63-206747 (JP, A) JP-A-55-125631 (JP, A) JP-A-51-135641 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB G03F 7/004 513 G03F 7/105 G03F 7/11

Claims (2)

(57) [Claims] (1) having a colored photosensitive layer on a support,
The colored photosensitive layer contains a photoreceptor, a binder, and a pigment,
Further, in a colored image forming material for transferring an image obtained by image exposure and development to an image receiving layer to obtain an image, at least one layer of heat is provided between the support and the colored photosensitive layer. A softening layer and / or a release layer is formed, and at least a surface of the thermal softening layer and / or the release layer which is in contact with the colored photosensitive layer is treated with a silane coupling agent and / or a titanate coupling agent. Image forming material. 2. A method for producing a colored image forming material, comprising forming a colored photosensitive layer by applying a colored photosensitive layer coating solution on a support, wherein the colored photosensitive layer coating solution comprises a photosensitive member, a binder, and a pigment. And at least one intermediate layer is formed between the support and the colored photosensitive layer by an intermediate layer coating solution, and at least the surface of the intermediate layer that is in contact with the colored photosensitive layer is a silane coupling agent. And / or a treatment with a titanate coupling agent.