JPH03279955A - Image forming material and production of image forming material - Google Patents

Abstract

PURPOSE:To prevent the adsorption, etc., which are the cause for staining by subjecting the pigments of a colored photosensitive layer to an anion treatment. CONSTITUTION:The pigments of the colored photosensitive layer of the image forming material which transfers the images obtd. by image exposing and developing and obtains transferred images are subjected to the anion treatment. For example, fiber Marseilles soap (sodium oleate soap), NS soap (half cured tallow sodium soap), FR-14 (potassium oleate soap), FR-25 (castor oil potassium soap), etc., are used as the anionic surfactant which can be used for the pigment treatment. The good images free from the staining are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an image forming material and a method for producing an image forming material. In particular, the present invention provides an image forming material which prevents scumming from occurring in the transferred image when the image is transferred to an image receiving layer to obtain the 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 to light and developed to obtain an image, and then transferred to obtain a transferred image, the non-image areas become stained with colorants, etc. Staining may occur.

This is thought to occur due to various reasons, but for example, when a release layer or heat softening layer is provided to efficiently transfer the formed image, the color that forms the colored photosensitive layer in these layers may Agents may get in there, which can cause stains.

For example, an image forming material with a structure in which a heat-softening layer is provided on one side of a support and a colored photosensitive layer (which may be composed of two layers, a colored layer and a photosensitive layer) is further provided on this layer is prepared. When doing so, it is common to form a colored photosensitive layer by coating 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,
A thermal drying step is generally required. However, some pigments, especially organic pigments, may adhere to the heat-softening layer when heated, and this may be caused by heating during the final image transfer.
This may result in re-transfer onto the surface of the transfer material such as paper, causing background stains.

[Problem that the invention seeks to solve]

As described above, conventional image forming materials have had the problem that background smear may occur in the final image.

The present invention is intended to solve this problem, and an object of the present invention is to provide a layer that easily adsorbs the pigment of the colored photosensitive layer, such as a heat softening layer, or Even when using pigments that are easily adsorbed by pigments, it is possible to obtain an image forming material that can prevent the above-mentioned adsorption that causes background smear and obtain good images without background smear. It is also an object to provide a manufacturing method for making such an imaging material.

[Means and effects for solving the problems] The above-mentioned object of the present invention is to have a colored photosensitive layer on a support, the colored photosensitive layer contains a photoreceptor, a binder, and a pigment, and In a colored image-forming material in which an image is obtained by transferring an image obtained by development to an image-receiving layer, the pigment in the colored photosensitive layer is anion-treated. , achieved.

Further, in a method for producing a colored image forming material in which a colored photosensitive layer coating liquid is applied onto a support to form a colored photosensitive layer, the colored photosensitive layer coating liquid contains a photoreceptor, a binder, and a pigment; And, it can be achieved by a method for producing an image forming material, which is characterized in that the pigment of the colored photosensitive layer is subjected to anion treatment.

Although the effect of the present invention is not necessarily clear, it is thought to be due to the following factors.

That is, it is thought that one of the causes of background smearing is the adsorption of the pigment to the thermally softened layer during the thermal process. Therefore, it is thought that the problem of scumming can be solved if pigments are treated in some way to control their adsorption properties. From this point of view, the inventors of the present invention have made extensive studies and have found that anion treatment among the vast number of treatment means is suitable for this purpose, and have completed the present invention. Therefore, the effect of the present invention is considered to be based on the change in adsorption of the pigment due to the anion treatment, but this is only an estimate, and the exact effect is unknown.

In any case, by performing pigment treatment by anion treatment, it has become possible to obtain a final image free of background stains.

The present invention will be explained in more detail below.

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

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

The binder is a binding agent in the photosensitive layer, and various polymer compounds can be used.

For example, a preferred binder may include a copolymer of vinyl acetate and vinyl versatate.

Other preferred binders that can be used in the present invention will be detailed later.

The colored photosensitive layer may be composed of two separate layers: a photosensitive layer (for example, consisting of a photoreceptor and a binder) and a colored layer (for example, consisting of a pigment and a binder). In that case, the layer order is arbitrary.

In a preferred embodiment of the present invention, the colored photosensitive layer on the support is formed on the support via an intermediate layer such as a heat-softening layer or a release layer. In particular, it is preferable to adopt a structure in which a heat-softening layer is formed on the support (preferably a release layer is further formed on this), and a colored photosensitive layer is formed on this.

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

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

Next, the image forming material of the present invention is image-exposed, developed, and the resulting image is transferred to obtain a transferred image.

For exposure and development, appropriate means can be used depending on the photoreceptor and the like.

In the image forming material of the present invention, the pigment in the colored photosensitive layer is anion-treated.

In the present invention, anion treatment refers to treatment with an anionic substance, typified by surface treatment with an anionic surfactant.

In the present invention, as the anionic surfactant that can be used for pigment treatment, various known anionic surfactants can be used, but specifically preferred ones include, for example, fiber Marcel soap ( Sodium oleate soap), NS soap (semi-hardened beef tallow sodium soap), FR14 (potassium oleate fm), F
R-25 (castor oil potash soap), Emar 0 (sodium lauryl sulfate), Emar 40 (sodium higher alcohol sulfate), Emar TD (triethanolamine lauryl sulfate), Emar AD-25 (sodium lauryl 6i acid), Neoperex No. 6 (sodium dodecylbenzenesulfonate), Perex NB-L
(sodium alkylnaphthalene sulfonate), Perex C3 (sodium dialkyl succinate), Emar 20C (sodium polyoxyethylene alkyl ether sulfate), Emar 20T (triethanolamine polyoxyethylene alkyl ether sulfate), Emar N
C (sodium polyoxyethylene alkylphenol ether sulfate), Electrostripper K (alkyl phosphate), Demol N (naphthalene sulfonic acid formalin condensate), Demol P (special carboxylic acid type polymer activator), In addition, Perex 5S-H, Nikkor SLS, Nikkor SSS,
Niracol ETC-3NEX and Niracol DDP-4 can be preferably used. Particularly preferably, Neoperex 6, Perex 5S-H, and Emar NC can be used.

As a pigment treatment method using an anionic surfactant, the most common and most preferable method is to form an interface and an active agent layer by washing the surface with an anionic surfactant solution.

The solvent for the surfactant is preferably water. The aqueous surfactant solution used for the treatment is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight.The anionic surfactant may be dissolved in any other solvent before use. When an organic solvent is used, for example, those exemplified as solvents that can be used in a coating solution for forming a colored photosensitive layer described later can be used. However, when an organic solvent is used, alcohols are preferable, and in particular, n -Butanol is preferred.

Pigments that have been subjected to anion treatment are thought to have a weakened affinity with intermediate layers such as the heat-softening layer and release layer 1 due to surface modification, and as a result, adsorption etc. are prevented. It is desirable to have a strong effect of weakening such affinity.

In the present invention, the term "pigment" refers to a coloring agent for forming a colored image.

Any of various pigments can be used as the coloring agent in the colored photosensitive layer, but in particular, when used for color proofing, the pigments are generally the usual colors required there, i.e., yellow, magenta,
Pigments with different tones such as cyan and blank are required.

Other metal powders, white pigments, fluorescent pigments, etc. can also be used. When the imaging materials of the present invention are applied to color proofs, for example for color image proofing, a number of pigments known in the art may optionally be used, such as those described below.

(C, I mean color index).

Victoria Pure Blue (CA 42595) Auramine (C, I 41000) Cathylone Brilliant Flavin (C, I Basic 13) Rhodamine 6GCP (C, I 45160'') Rhodamine B (C, I 45170) Safranin OK2
O: 100 (C,I 50240)Erioglaucine 8GF (C,I 21105) Benzidine Yellow 4T-564D (C,121095) Shimla Furth Red 4015 (C,I 12355) Lionol Red 7 B12O3 (C,I 15830
) First Gen Blue TGR-L (C, I 74160) Lionor Blue SM (C, I 26150'') Mitsubishi Carbon Black M A-100 Mitsubishi Carbon Black #30. #40. #50 In the practice of the present invention, colored photosensitive The content of the pigment in the layer can be determined in consideration of the target optical density and the removability of the colored photosensitive layer with respect to a developer.

In the present invention, The pigment content is The content 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 explained. Various photosensitive materials can be used as the photoreceptor. For example, when such a photoreceptor is irradiated with actinic rays, its molecular structure undergoes a chemical change in a short period of time, and its solubility in a solvent changes.
It includes all compounds such as monomers, prepolymers, or polymers whose exposed or unexposed portions are dissolved and removed when a certain type of solvent is applied.

Examples of photoreceptors that can be used include photoreceptors of the so-called negative/positive type, which have reduced correction in the exposed area, such as photocrosslinkable photoreceptors such as those made by esterifying polyvinyl alcohol with cinnamic acid. There are resin systems, systems in which diazonium salts and their condensates are mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc., and systems in which aromatic azide compounds are used as photocrosslinking agents and are mixed with binders such as cyclized rubber. Furthermore, photosensitive resins using photoradical polymerization or photoionic polymerization can also be used.

Furthermore, as a so-called positive-positive type composition that increases the solubility of the exposed area, there is, for example, a photosensitive composition containing 0-quinonediazide as a photosensitizer, and specifically, 1.2-
benzoquinonediazide-4sulfonyl chloride, 1.
Compounds obtained by condensing 2-naphthoquinonediazide-4-sulfonyl chloride, 1.2-naphthoquinonediazide-5-sulfonyl chloride, 1.2-naphthoquinonediazide-6-sulfonyl chloride with a hydroxyl group- and/or amino group-containing compound are preferably used. .

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, hydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcin benzaldehyde condensation resin, and pyrogallol acetone condensation resin. Examples of amino group-containing compounds include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4-diaminobenzophenone, and 4°4-diaminodiphenylamine.

Regarding the above 0-quinonediazide compound, J, K
“Light 5-sensitive Sys” by osar
tem'' (Wiley & 5ons, New Year
K+ 1965) and Powdered Ice, Dry Photosensitive Polymer Paste (Kodansha, 1977).

In addition, positive-positive type products include: ■ a compound that can generate an acid when irradiated with actinic rays, ■ a compound that has at least one bond that can be decomposed by an acid, and ■ a novolak resin that contains two or three different types of phenols. A photosensitive composition can also be used.

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

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

The binder contained in the colored photosensitive layer can be any binder as long as it can function as a binder, such as a polymer compound that is film-forming and solvent-soluble, and preferably dissolves or swells in an alkaline developer. can be used.

Specific examples of such polymer compounds include the following -
Examples include polymer compounds containing a structural unit having an aromatic hydroxyl group represented by Monka (I) in its molecular structure.

General formula (I) In general formula (I), R'' and R12 each independently represent a hydrogen atom, an alkyl group, or a carboxylic acid group. RIf
f represents a hydrogen atom, a halogen atom, or an alkyl group; R'' represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group; X represents a divalent organic group connected to a nitrogen atom and an aromatic carbon atom; n represents O or 1. Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specifically, examples of monomers forming the structural unit represented by the above-mentioned pattern (I) include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-( meth)acrylamide, N-(4
Examples include (meth)acrylamide monomers such as -hydroxynaphthyl)-(meth)acrylamide; 0-2m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers. Preferably o-, m- or P-hydroxyphenyl (meth)acrylate monomers, N-
(4-hydroxyphenyl)-(meth)acrylamide monomer, 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 general formula (1) and the following monomers as the binder.

R’S Acrylonitrile: CH,=CN I5 1 Acrylic acids: CH.

R"-OH In each of the above formulas, R'5 represents a hydrogen atom, an alkyl group, or a halogen atom, and R16 represents an alkyl group, a phenyl group, or a naphthyl group.

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

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

In addition to the structural units described above, the above-mentioned acrylic acids such as acrylic acid or methacrylic acid may be copolymerized to form structural units in the polymer compound that is the copolymer, for the purpose of finely adjusting the developability.

In that case, the proportion of the copolymer of acrylic acids in the polymer compound is 0, considering the development latitude.
-20 mol% is preferred, and 0-10 mol% is most preferred.

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

Specific examples of such polymer compounds include copolymers having the following structure.

(Weight average molecular weight: 1,000-30.000>
1: m: n=(1-25): (5-40
): (50-95) In the image forming material of the present invention, the following -
A polymer compound having a carboxylic acid vinyl ester polymerized unit shown by a hole in its molecular structure can also be preferably used.

RCOOC)l=cHz However, R represents an alkyl group having 1 to 17 carbon atoms.

Any polymeric compound having the above structure can be used, but as the carboxylic acid vinyl ester monomer for constructing the polymerized unit indicated by the above-mentioned symbol, the following examples are preferable. The name and chemical formula are also shown.

■Vinyl acetate CH3COOCH= CH2
■Vinyl propionate CHHzCHzCOOCH=CFl
z■Vinyl butyrate CH3(CH2)ZCOO
CH=CH2■ Vinyl pivalate (CHi)zC
COOCH=CHz■Hinyl cafuroate CH, (CHz
), C00CH=CHz ■Vinyl caprylate CH
s (C)I Z) 6COOCH= CHz ■Vinyl caprate CH3 (CHz)scOOcH=cH
z■Vinyl laurate CH3 (CH2) +oC
OOCH=CHz■Vinyl myristate CHt(C
Hz) +□C00CH= CHz [Phase] Vinyl palmitate (H) (CJ) +4COOCH=CHz ■ Vinyl stearate CH3 (CHZ) l 6COO
CH= CIl□@vinyl versatate CH3 R' CC00CR=CHz 2 (R1 and R2 are alkyl groups, and the sum of their carbon numbers is 7. That is, the form is R'+R''=CJ+i) Carboxylic acid vinyl ester As the monomer, those having 1 to 4 carbon atoms constituting the main chain of carboxylic acid are more preferable.Vinyl acetate is particularly preferable.

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

The polymer compound may be a polymer obtained by polymerizing one type of carboxylic acid vinyl ester (or a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl ester), or a polymer obtained by copolymerizing this with carboxylic acid vinyl ester. It may also be a copolymer with other monomers in any component ratio.

Examples of monomer units that can be used in combination with the polymerized units indicated by the above-mentioned holes include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, Styrenes such as P-methylstyrene and P-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, such as diethyl maleate and maleic acid. Diesters of unsaturated dicarboxylic acids such as dibutyl acid, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic dodecyl acid, 2-chloroethyl acrylate,
α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, and ethyl methacrylate; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide; e.g. acrylic Anilides such as anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, vinyl ethers such as methyl vinyl ether, ethyl vinyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride , vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1°1-dimethoxyethylene, 1,2-dimethoxyethylene, 1.
1-dimethoxycarbonylethylene, 1-methyl-1-
Ethylene derivatives such as ditroethylene, such as N-vinylpyrrole, N-vinylcarbazole,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylpyrrolidone, and N-vinylpyrrolidone. These vinyl monomers generally exist in a polymer compound with a structure in which unsaturated double bonds are cleaved.

When using the polymer compound represented by the above-mentioned pattern in the present invention, it is particularly preferable to use a polymer compound having a vinyl acetate polymerization unit in its molecular structure.

Among them, 40 to 95 wt% of vinyl acetate polymer units
having a number average molecular weight (MN) of 1,000 to 1
00.000, weight average molecular weight (MW) is 5,
000 to 500,000 is preferred.

More preferably, vinyl acetate polymerized units (especially 40
~95wt%) and polymeric compounds having carboxylic acid vinyl ester polymerized units with a longer chain than vinyl acetate, especially those with a number average molecular weight (MN) of 2.000 to 60,
000, weight average molecular weight (MW) is 10,000-15
0,000 is preferred.

In this case, the monomer that copolymerizes with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer that can form a copolymer, such as among the monomers listed above. You can arbitrarily choose from.

Copolymers that can be used as polymer compounds in the present invention are listed below by indicating their monomer components. However, it goes without saying that the invention is not limited to the following examples.

■Vinyl acetate-acrylic acid ester ■Vinyl acetate-maleate ester ■Vinyl acetate-ethylene ■Vinyl acetate-vinyl carboxylate ester ■Vinyl acetate-styrene ■Vinyl acetate-crotonic acid ■Vinyl acetate-maleic acid ■Vinyl acetate-2-ethyl Hexyl acrylate ■Vinyl acetate-2-ethylhexyl maleate [Phase] Vinyl acetate-Methyl vinyl ether ■Vinyl acetate-Vinyl chloride @ Vinyl acetate-N-vinylpyrrolidone ■Vinyl acetate-Vinyl propionate [Phase] Vinyl acetate-Vinyl pivalate ■Hinyl acetate Vinyl acetate ■ Vinyl acetate - Hinyl laurate) Lt ■ Vinyl acetate - Hinyl stearate [Co., Ltd.] Vinyl acetate Rubersatate - Ethylene [Co., Ltd.] Vinyl acetate Rubersatic acid vinyl-2-ethylhexyl acrylate [ Phase] Vinyl acetate - Vinyl versatate - Vinyl laurate - Vinyl acetate - Vinyl versatate - Crotonic acid @ Vinyl propionate - Vinyl versatate - Vinyl propionate - Vinyl versatate - Crotonic acid [Phase] Pivalic acid - Vinyl-maleic stearate In the present invention, a novolac resin can also be used as a binder.

Novolak resins are generally obtained by polycondensation of at least one type of phenol and an active carbonyl compound, and any of these novolak resins can be used.

The above-mentioned phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specific examples of such phenols include, for example:
Phenol, 0-cresol, m-cresol, P-cresol, 3.5-xylenol, 2.4-xylenol, 2.5-xylenol, carvacrol, thymol,
Catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, alkyl group (1 to 8 carbon atoms)
Examples include substituted phenols.

The active carbonyl compounds include, for example, aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Examples of the novolak resin include phenol formaldehyde novolac resin, m-cresol formaldehyde novolak resin, phenol/m-cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, m-cresol・p-cresol/formaldehyde copolycondensate resin, 0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/m −
Cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/m-cresol/p
-Cresol/formaldehyde copolycondensate resin, etc. can be mentioned.

A preferred novolac resin is a phenol formaldehyde novolac resin having a weight average molecular weight MW of 350.
Preferably, the number average molecular weight MN is in the range of 0 to 500, and the number average molecular weight MN is in the range of 1000 to 200.

The molecular weight of the polymer compound in this specification, including the molecular weight of the novolak resin, is measured by GPC (gel permeation chromatography). Calculation of the number average molecular weight MN and weight average molecular weight MW is based on Morio Seiji, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan” 800.
The method described on pages 805 to 805 (1972) is used to level out the peaks of the oligomer region (connecting the centers of the peaks and valleys).

In addition, in the novolac resin, pyrolysis gas chromatography (PGC) is used as a method for confirming the quantitative ratio of different phenols used in the synthesis thereof.

The principle of pyrolysis gas chromatography is
If the equipment and experimental conditions are specified, for example, in the Journal of the Chemical Society of Japan,
New Experimental Chemistry Course” Volume 19, Polymer Chemistry (I) 47
The method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in pages 4 to 485 (published in Marukubi 1978), etc., and the method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in "Analytical Chemistry" Vol. 18 by Morio Seiji, Takashi Naka, and Masayuki Tanaka. , pp. 47-52 (1969).

In the present invention, the colored photosensitive layer is coated with a novolac resin (component (b)
)) and a polymer compound (referred to as component (c)) having a carboxylic acid vinyl ester polymerized unit represented by the above general formula in its molecular structure,
(b) / (c) It is preferable that the content is in a weight ratio range of -5/95 to 80/20.

This range is preferable in terms of color reproducibility, thermal deformation (dimensional deviation), and color fastness. Component (b) (c
A particularly preferred ratio of ) is (b)/(c) = by weight
It is in the range of 10/90 to 60/40.

Further, in the present invention, other polymeric compounds that can be used as a binder for the colored photosensitive layer include (meth)
Sulfoalkyl esters of acrylic acid (co)polymers, vinyl acetal (co)polymers, vinyl ether (co)polymers, acrylamide (co)polymers, styrene (co)polymers, cellulose derivatives, etc. may also be mentioned. .

The thickness of the colored photosensitive layer in the image forming material of the present invention can be appropriately determined depending on the target optical density, the type and content of the colorant used in the colored photosensitive layer, and the like. Within the allowable range, the thinner the colored photosensitive layer is, the higher the resolution and the better the image quality. Therefore,
The film thickness is preferably 0.1 g/rrf to 5 g/rrf
It is usually used within the range of

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

Here, an organic solvent can be used as a solvent to constitute the coating liquid. In carrying out the present invention, any organic solvent can be used as the colored photosensitive layer coating solution, and for example, all of the various known organic solvents can be used. Examples of organic solvents that can be used include hydrocarbons such as n-hexane, cyclohexane, n-pentane, benzene, toluene, and xylene, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and t-butyl alcohol. , sec~phthyl alcohol, isobutyl alcohol, n-butyl alcohol, isobutyl alcohol, n-butyl alcohol, 1
-Alcohols such as pentanol, 2-pentanol, 1-hexanol, ketones such as acetone, cyclohexanone, methyl ethyl ketone, methyl-〇-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, diethylene glycol Diethylene glycols such as dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monoethyl ether; other esters such as methyl lactate, ethyl lactate, methyl propionate, methyl butyrate, and ethyl acetate; nitrites such as acetonitrile and propionitrile; and others 1,4 -Dioxane, dimethylformamide, dimethyl sulfoxide, methylene chloride, chloroform, carbon tetrachloride, etc. can be mentioned.

Among these, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones, and esters are preferably used, and particularly preferred are cyclohexanone, toluene, and methyl lactate.

When carrying out the present invention, plasticity and coating properties improvers and the like may be added to the colored photosensitive layer, if necessary.

Various low-molecular compounds such as phthalate esters, triphenyl phosphates, and maleate esters can be used as coating agents, and surfactants such as fluorine-based surfactants, ethyl cellulose polyalkylene ether, etc. can be used as coating properties improvers. Examples include representative nonionic surfactants.

When constituting the image forming material of the present invention, the colored photosensitive layer can be divided into two layers: a colored layer made of a colorant and a binder, and a photosensitive layer made of a photosensitive composition. In this case, it does not matter which layer is placed on the support side.

The colored imaging materials of the present invention can be embodied as color proofs.

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

Although any support can be used to constitute the image forming material of the present invention, a transparent support is preferably used. As the transparent support, a polyester film, especially a two-wheel stretched polyethylene terephthalate film, is preferable from the viewpoint of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film, polyethylene film, polypropylene film, polyethylene film, etc. may also be used. obtain.

The image forming material can be used to transfer an image to a transfer material. At this time, in order to efficiently transfer the image onto the material to be transferred and to facilitate peeling off the support after image transfer, a release layer (a release layer is used to remove the surface of the support) between the support and the colored photosensitive layer is used. It is preferable to provide an intermediate layer such as a heat softening layer or a heat softening layer.

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

Furthermore, silicone resin or fluororesin may be added to melamine resin or polyacrylate urethane resin.

In addition, polypropylene film, polyethylene film, etc. exhibit good mold release properties without special mold release treatment, so in a preferred embodiment, the film is thinner than the thickness of the support.
A polypropylene layer or a polyethylene layer can be provided as a release layer.

The method for forming a polypropylene layer or polyethylene layer on a support is as follows: (1) A solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. After applying these adhesives on a support and drying with hot air or heating, a polypropylene film or a polyethylene film is overlaid and laminated by pressing under heat.
So-called dry lamination method; (2) Using a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and acrylic ester, polyamide resin, petroleum resin, rosin, wax, or a mixture thereof as an adhesive, these adhesives After applying the material onto a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc. while keeping it in a molten state by heating it as it is,
The so-called hot-melt lamination method, in which polypropylene or polyethylene films are immediately laminated together and laminated by heating at a high temperature if necessary and then cooling; (3) The polypropylene or polyethylene is kept in a molten state and then extruded. This is the so-called extrusion lamination method, in which the film is extruded into a film, and while it is still in a molten state, a support is bonded and laminated; Examples include a so-called coextrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film by multiple moldings using polypropylene or polyethylene in a molten state.

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 thermally softened layer will be described.

The thermosoftening layer has a property of softening at the temperature during thermal transfer, and can be formed from a thermoplastic resin. The thermoplastic resin has a softening point of 130°C to 150°C.
C is preferred. The softening point temperature mentioned here is VIC
This is the AT softening point or the value shown by the ring and ball method. In the present invention, specifically, the following resins can be mentioned as preferred resins.

Polyolefins such as polyethylene and polypropylene.

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

PVC.

Vinyl chloride copolymers such as vinyl chloride and vinyl acetate.

Polyvinylidene chloride.

Vinylidene chloride copolymer.

polystyrene.

Styrene copolymers such as styrene and maleic anhydride.

Polyacrylic acid ester.

Polyester resin.

Polyurethane resin.

Acrylic ester copolymers such as acrylic ester and vinyl acetate.

Polymethacrylic acid ester.

Methacrylate ester 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.

Chlorinated rubber.

Polyethylene glycol.

Polyvinyl alcohol hydrozine phthalate.

cellulose derivative, cellulose acetate phthalate,
Cellulose acetate succinate.

Schlatsk.

wax.

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

The thickness of the thermally softened layer is suitably in the range of 1 to 50 μm, particularly preferably in the range of 5 to 30 μm.

The release layer can be provided on the heat-softening layer by applying a solution or emulsion of the release layer resin dissolved in an organic solvent onto the heat-softening layer, or by applying a polypropylene film or a polyethylene film. Examples include a method of laminating on a heat softening layer.

The image forming material of the present invention is exposed and developed to form an image area, and at least the formed image area is transferred to a transfer material to obtain a transferred image.

For example, when the method is implemented as a multicolor image forming method, the basic method can be broadly divided into the following methods (1) and (II).

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

Next, a second colored image-forming material having a colored image-forming layer of a second color different in tone from the first color (both colored image-forming layers are placed on the first-colored colored image layer on the transfer material). alignment image of the second color film original that corresponds to the second color (generally called a registration mark image is used)
is registered with the first color registration mark image, image exposure is performed through the second color film original, followed by development processing to obtain a two color matched image on the transferred material. Thereafter, similar processing is performed for the third and fourth colors to obtain a multicolor image.

This method is known from Japanese Patent Publication No. 47-27441, Japanese Patent Publication No. 56-501217, etc.

(n) Forming a first color colored image on a first color colored image forming material, transferring at least the colored image to a transfer material, and peeling off the support. Further, after forming a second color colored image on the second color colored image forming material, the second color register mark direct image formed accordingly is registered with the first color register mark image on the transfer target material. while transferring a second color colored image onto the first color colored image and peeling off the support to obtain a two color matched image. Similarly, colored images of the third color and the fourth color are also transferred onto the transfer material to obtain a multicolor image. In some cases, this multicolor image may be indirectly transferred onto another transfer material,
Multicolor images may also be obtained.

This type of method is disclosed in JP-A-47-41830, JP-A-59-97140, JP-A-60-23649 and US Pat. No. 3,775,113.

Imaging materials are typically exposed imagewise through a color separation mask or the like and then developed to form an image.

At this time, an embodiment may be adopted in which only the image portion from the image obtained on the support is directly transferred and laminated onto the transfer material. That is, in one preferred embodiment, only the colored image layer that substantially forms the image is transferred and laminated.

In this case, in order to efficiently transfer the image onto the surface to be transferred and to facilitate the peeling off of the support after image transfer, the surface of the support may be subjected to a release treatment using an appropriate perishable 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 appropriate light depending on the colored photosensitive layer, particularly depending on the photoreceptor, and then developed to obtain an image. Any developer can be used as long as it has a developing action to develop the material to be processed. Preferably, a developer containing an alkaline agent and an anionic surfactant is used.

Usable alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

Sodium or ammonium salts of secondary or tertiary phosphates, sodium metasilicate, sodium carbonate.

Inorganic alkaline agents such as ammonia, (2) Mono-, di-, or trimethylamine, mono-, di-,
or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropylamine, ethyleneimine.

Examples include organic amine compounds such as ethylenediimine.

In addition, as anionic surfactants that can be used, (1)
Higher alcohol sulfate esters (e.g., sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfuric acid alkyl sulfate, etc.), (2) Salts of aliphatic alcohol phosphate esters (e.g.,
(3) Alkylaryl sulfonate salts (eg, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, etc.).

dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (5) Sulfonic acid salts of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) ) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (for example, formaldehyde condensates of sodium dibutylnaphthalene sulfonate, etc.).

Alkaline agents and anionic surfactants are optional. Can be used in combination with

〔Example〕

Examples of the present invention and comparative examples will be described below.

It should be noted that, as a matter of course, the present invention is not limited only to the embodiments described below, but can take various forms.

Example 1 In order to obtain the image forming material of the present invention, pigment treatment (anion treatment) was carried out as follows.

First, a 1% by weight aqueous solution of Neoperex NO.6 was prepared, and four 150 d aqueous solutions were taken. For each 150 ml of each aqueous solution, add cyan (Lionol Blue FG)
-7330, manufactured by Toyo Ink Co., Ltd.), magenta (Lionol Red 68 PG-4219X, manufactured by Toyo Ink Co., Ltd.), yellow (Lionol Yellow FG 1206, manufactured by Toyo Ink Co., Ltd.), black (carbon black old = 100, manufactured by Mitsubishi Kasei Co., Ltd.) 3 g of each pigment was added separately, stirred with a magnetic stirrer for 20 minutes, and then filtered and dried. Drying is done by air drying for 1 day, then by heating under suction (100°C) for 2 days.
I let it dry for an hour and a half. With these operations,
Four colored pigments treated with Neopelex were obtained as pigments for dispersion.

In order to form a color image using these pigments, colored photosensitive layer dispersions were prepared according to the following formulation.

Anion Color (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) 15.3
6 g of the above Neopelex treated pigment (cyan) 1.1
0g cyclohexanone 71.47
g anion or mine )1.2
-Naphthoquinone diazide-4-sulfonic acid-P-cresol formalin ester polymer 2.37g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 15.3
6g Neoperex treated pigment (magenta) 1.1
0g cyclohexanone 71.47
g anion color yellow 1.2-
Naphthoquinonediazide-4 sulfonic acid-p-cresol formalin ester polymer 2.37g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 15.3
6g of the above Neopelex treated pigment (Yellow H, 10g
Cyclohexanone 71.47 g
Anion Bootta 1.2-naphthoquinone diazide-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. 2
1 g of the above Neopelex treated pigment (Black H, 85
g Cyclohexanone 71.47g
In addition, a support shown below was separately prepared.

That is, an undercoat layer coating solution having the following composition was applied onto a polyethylene terephthalate film so that the dry film thickness was 10 μm to form a heat-softening layer.

Modified polypropylene solution solid concentration 20% by weight (product name: UNISTOL Q manufactured by Mitsui Petrochemicals) Next, a release layer solution having the following composition was applied onto this heat-softened layer so that the dry film thickness was 1 μm. A release layer was formed.

Product name: Si coat 900A solution solid content concentration 30% by weight This 12
The support was heat-cured at 0°C for 3 minutes to produce a support having a release layer and a heat-softening layer.

The four colored photosensitive layer dispersions obtained earlier were coated on the support having the release layer and heat softening layer obtained above so that the dry film thickness was 1 μm, and then dried. .

In this way, colored image forming materials of four colors were created.

Color separation mesh positive films of each color were superimposed on the polyethylene terephthalate film surface of the four-color colored image forming material obtained above, image exposure was performed for 20 seconds from a distance of 50 cm using a 4 kW metal halide lamp, and the following developer was added to Development was performed by dipping for a second to form a four-color colored image.

<Developer> NazCO 315g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50g Distilled water 1000g Next, the image surface of the black image and art paper were brought into close contact and heated at 80°C.
5kg/c111 between a pair of nip rolls heated to
The support was peeled off after passing at a speed of 50 cm/min under pressure conditions of . Peeling was easy and only the black image area was transferred onto the art paper.

Subsequently, colored images were transferred in the order of cyan, magenta, and yellow, thereby obtaining a color proofing image consisting of four colors on art paper.

Furthermore, although the configuration was the same as above, it was also carried out using Pellex SSH and Emal NC as anionic surfactants, and the same treatment was performed for each.
Color proofing images consisting of four colors using each anion-treated pigment were obtained.

The color proofing image obtained in this example is
All of them have excellent color reproducibility and can produce transferred images with little color cast (background stain) in non-image areas.
Furthermore, the transferred image was extremely similar to the actual printed matter.

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

Cyan 1.2-naphthoquinonediazide-4-sulfonic acid-p-cresol formalin ester polymer 2.37g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 15.3
6g Lionol Blue FC-7330 (manufactured by Toyo Ink Co., Ltd.) Cyclohexanone color (magenta) 1.2-naphthoquinone diazide-4 sulfonic acid-p-cresol formalin ester polymer vinyl acetate-ruversatate (80:20 parts by weight) Copolymer (49.7% methanol solution) Lionol Red 68 FG-4219 (manufactured by Toyo Ink Co., Ltd.) Cyclohexanone color Yellow 1.2-naphthoquinone diazide-4 Sulfonic acid-p-cresol formalin ester polymer Vinyl acetate -Vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 1.1g 71.47g 2.37g 15.36g 1.1g 71.47g 2.37g 15.36g Lionol Yellow FC, 1206 (manufactured by Toyo Ink Co., Ltd.) 1.1g cyclohexanone 71.47g color
Black 1.2-naphthoquinonediazide-4 sulfonic acid-P-cresol formalin ester polymer 2.19g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 14.2
1 g Carbon black M A-100 (manufactured by Mitsubishi Kasei) 1.85 g Cyclohexanone 72.05 g The colored photosensitive layer dispersion obtained here was used in Example 1.
The dry film thickness is 1μ on the support having a release layer and a heat softening layer.
After coating to give a coating thickness of m, it was dried to produce colored image forming materials in four colors.

The four-color image forming material obtained above was exposed and developed in the same manner as in Example 1, and this was transferred onto art paper to form a color proofing image consisting of four colors on the art paper. Obtained.

The color proofing image obtained by this method had a color cast (background stain) in the non-image area, and the color reproducibility of the image was poor.

〔Effect of the invention〕

As described above, the image forming material of the present invention has the effect that a good image without scumming can be obtained even when a heat softening layer or the like is provided, and the image forming material of the present invention The method of manufacturing the material is one that can provide such advantageous imaging materials.

Claims (1)

[Scope of Claims] 1. A colored photosensitive layer is provided on a support, and the colored photosensitive layer contains a photoreceptor, a binder, and a pigment, and the image obtained by image exposure and development is used as an image. 1. A colored image-forming material that is transferred to an image-receiving layer to obtain an image, characterized in that a pigment in the colored photosensitive layer is anion-treated. 2. A method for producing a colored image forming material in which a colored photosensitive layer coating liquid is applied onto a support to form a colored photosensitive layer, the colored photosensitive layer coating liquid containing a photoreceptor, a binder, and a pigment; and a method for producing an image forming material, characterized in that the pigment of the colored photosensitive layer is subjected to anion treatment.