JPH1033968A - Dispersant assisting agent, solid dispersing composition, photosensitive composition, and photographic material for color-proofing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant assisting agent with excellent dispersing property and dispersion stability and excellent affinity with various kinds of materials by using a compound with a specified structure as the dispersant assisting agent. SOLUTION: As a dispersant assisting agent, a composition having a chemical formula 1 is used (wherein R1 , R2 , R7 , R8 respectively stand for hydrogen atom, linear or branched 1-30C alkyl groups and which may have substituents, and alicyclic hydrocarbon groups which may have substituents; R3 -R6 for the groups having the constitutional formula 2 wherein R9 -R12 stand for the group defined as same as R1 ; n for zero or higher integer; m for one or higher integer). This dispersant assisting agent is a solid in an organic solvent, preferably a coloring agent, and is excellent to produce a dispersion liquid of a pigment and/or a dye. Moreover, in the case the dispersion liquid is used as a coating liquid, a photosensitive composition having high sensitivity and excellent development property can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dispersion aid useful as an aid for dispersing solid particles in a liquid, in particular, an organic liquid, a solid dispersion composition containing the dispersion aid, and a color printing method. The present invention relates to a photosensitive composition applicable to a color proof for color proofing.

[0002]

2. Description of the Prior Art Dispersing a solid finely in a liquid and keeping the state stable for a long period of time is indispensable for producing paints and inks. In recent years, in order to improve production efficiency, for example, it is sometimes necessary to make several kinds of products in which the same solids are dispersed and the added polymers are different. In many cases, the materials are prepared in advance, and then the necessary materials are added later to make various types of finished products. For example, JP-A-46-7294 describes an example in which a solid dispersion is prepared using a dispersing agent having various structures, and JP-B-63-30057 and JP-B-57-25251 describe: Dispersants of a particular structure and solid dispersions of organic liquids containing the same are described. However, it is very difficult to finely disperse solids in a liquid and to keep the state stable for a long period of time.For paints and inks, these manufacturers have tried and error based on empirically favorable combinations. It is currently being manufactured. When an intended composition is prepared by adding a polymer or other solvent to the dispersion thus prepared, the fine dispersion state is destroyed depending on the type of the compound to be added, that is, the solid in the dispersion is Are often settled, and even if the dispersing aid or dispersing agent described in the above patent is used, a solid dispersion having satisfactory dispersibility and its stability may not be obtained. There has been a problem that there are many surfaces lacking in solubility.

In recent years, a photosensitive composition containing a colorant has been increasingly used for producing a color proof photosensitive material for color proofing in color printing and a liquid crystal color filter. For example, for color proofing,
JP-A-1-169449 and JP-A-1-169450 disclose a colored image formed by exposing and developing an image-forming material having a colored photosensitive layer comprising a colorant and a photosensitive composition to an image area. An image forming method for forming an image by transferring only an image is described.
No. 54, an image forming material containing a quinonediazide, an acid-decomposable composition and a positive photosensitive composition having a vinyl carboxylate polymer-based binder is exposed and developed to form an image area, An image forming method for forming an image by transferring only an image is described.
No. 76754 discloses a photosensitive material having a photopolymerizable negative photosensitive composition, and JP-A-2-173645 discloses a photosensitive material.
Forming an image area by exposing and developing a photosensitive material having a negative photosensitive composition of diazo type and / or azide type;
An image forming method in which an image is formed by transferring only an image portion is described. In addition, it is also known that a photosensitive liquid in which a colorant is dispersed is used for a photoresist (such as production of a liquid crystal color filter).

These photosensitive compositions are coated on a support,
After drying and forming a photosensitive film, it is often used after performing exposure and development processing, but during the development processing, the colorant in the non-image area may remain on the support without being completely removed. This is, for example, in the case of a color proofing material,
Not only can the desired image pattern and hue not be obtained, but the colorant adheres to the transport rollers in the development processing device,
This causes the quality of the color proof to deteriorate in the continuous development processing, such as staining the surface of the photosensitive layer of the color proof to be developed next.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a dispersion aid having good dispersibility and dispersion stability, and improved compatibility with various materials. And a solid dispersion composition using the dispersing agent. Another object of the present invention is to provide a photosensitive composition having high sensitivity and excellent developability when used as a coating liquid.

[0006]

The above object of the present invention has been attained by the following constitutions.

(1) A dispersing aid represented by the following general formula (1):

[0008]

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R ₁ , R ₂ , R ₇ and R ₈ each represent a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent, and each has a substituent. May represent an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group,
R _{3 to} R ₆ represent the following structural formulas, and R _{9 to} R
₁₂ has the same meaning as R ₁ , n represents an integer of 0 or more, and m represents an integer of 1 or more.

[0010]

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(2) A dispersing aid represented by the following general formula (2).

[0012]

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A is a linear or branched alkyl group which has at least three hydroxyl groups and may have a substituent,
Or a residue of an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group which may each have a substituent;
_{13 to} R ₂₁ are each a hydrogen atom, a linear or branched alkyl group which may have a substituent having 1 to 30 carbon atoms, an alicyclic hydrocarbon group which may have a substituent, It represents an aromatic hydrocarbon group and a heterocyclic group, and x, y and z are each an integer of 1 or more, and each represents an integer whose sum is 5 or more.

(3) A solid dispersion composition comprising at least one compound selected from the compounds represented by the general formulas (1) and (2).

(4) A photosensitive composition comprising at least one compound selected from the compounds represented by formulas (1) and (2) and a solid.

(5) A light-sensitive material for color proof, comprising using the above-mentioned light-sensitive composition.

That is, the present inventors have found that solids have good dispersibility,
By using a novel dispersing agent that can stably maintain a fine dispersion state for a long period of time, the knowledge that a solid dispersion composition having excellent solid dispersibility and dispersion stability can be obtained, This has led to the present invention. In addition, even when a target composition is prepared by adding various materials later, there is also an effect that the material is compatible with a wide range of materials and a finely dispersed state is maintained. Further, by using the solid dispersion composition in a photosensitive coating solution, it also has excellent developability.

Hereinafter, the present invention will be described in detail.

[1] Dispersing Aid In the dispersing aid represented by the general formula (1), R ₁ , R ₂ ,
R ₇ and R ₈ are each a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group which may have a substituent. , An aromatic hydrocarbon group and a heterocyclic group.

Examples of the linear or branched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a butyl group,
t-butyl group, n-hexyl group, n-octyl group, n-
Examples include a stearyl group, a 4-octyl-octadecyl group, a 4-hydroxy-octadecyl group, a 4-methoxyoctyl group, and a 5-nitro-nonyl group. Examples of the alicyclic hydrocarbon group include a cyclohexyl group and a methylcyclohexyl group. , A hydroxycyclohexyl group, a cyclopentyl group, a cyclooctyl group, an ethylcyclohexyl group, a 1-cyclohexenyl group, and the like. Examples of the heterocyclic group include a 2-furyl group, a 2-pyrrolyl group, a 2-pyridyl group, a 4-pyridyl group, a 2-quinolyl group, and a 4-hydroxy-2- group. Examples thereof include a quinolyl group, a 4-quinolyl group, a furfuryl group, and a 2-thienyl group.

Preferred examples of R ₁ , R ₂ , R ₇ and R ₈ are a hydrogen atom and a linear or branched alkyl group having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and 1 to 18 carbon atoms.
And 4 is more preferably a hydrogen atom and a methyl group. Further, n is an integer of 0 or more, and m is an integer of 1 or more, preferably 10 or more.

R ₁ , R ₂ , R ₇ , R ₈ , a substituent which can be substituted for the above-mentioned linear or branched alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group; The substituent atom is not particularly limited, but includes, for example, an amino group, an alkylamino group, a halogen atom such as a chlorine atom and a bromine atom, a hydroxy group, an alkoxy group, a nitro group, an amide group, an alkylamide group, a carboxyl group, and a sulfonic acid group. And a carboxylic acid ester group such as a sulfonamide group and a methoxycarbonyl group; a substituted or unsubstituted aromatic hydrocarbon group; and a heterocyclic group.

R _{3 to} R _{6 each} have the following structural formula:

[0024]

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Wherein R _{9 to} R _{12 in the} above structural formula have the same meanings as R ₁ . R ₉ and R in the linking group of R ₄ and R ₅
Depending on ₁₀ , R ₄ and R ₅ may be a random bond having an irregular arrangement order, an alternate bond in which two types of connecting groups are alternately arranged, or a block bond in which the same type of connecting group is long and continuous.

In the dispersing aid represented by the general formula (2), A has at least three hydroxyl groups, a linear or branched alkyl group which may have a substituent, or each has a substituent. Represents a residue of an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group which may be represented by the above-mentioned alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group; It has the same meaning as R _{1 in} (1), but is preferably a residue from trimethylolpropane or glycerin. Further, x, y and z are each an integer of 1 or more, and each represents an integer whose sum is 5 or more, preferably each is 5 or more, particularly preferably each is 10 or more.
_{13 to} R ₂₁ have the same meaning as R ₁ described above.

The following are typical specific examples of the dispersing aid represented by the general formulas (1) and (2), but the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[2] Solid dispersion composition The dispersion aid represented by the general formula (1) or (2) may be a solid, preferably a colorant, especially a pigment and / or dye in an organic solvent described below. Although it has a very excellent effect in producing a dispersion, it has a general formula (1) or (2)
(Hereinafter, referred to as the compound of the present invention) may be used alone or as a mixture.

The colorant dispersion (solid dispersion composition) can be obtained by any conventional and known method. Thus, the colorant, the organic solvent and the compound of the present invention are mixed in any order, and then the mixture is subjected to mechanical treatment to reduce the particle size of the colorant, such as ball milling, bead milling, gravel milling. Alternatively, the dispersion liquid is obtained by applying a plastic roller or the like. Optionally, the colorant can be treated independently or mixed with an organic solvent to reduce the particle size of the colorant, followed by the addition of one or more other components and subsequent And stirring the mixture to obtain a dispersion. A colorant dispersion containing the finely dispersed colorant having a small particle diameter and at least one or more compounds of the present invention can be obtained. The amount of the compound of the present invention present in the colorant dispersion is not particularly limited,
0.1 to 60% by weight based on the weight of the colorant is preferable,
More preferably, it is 2 to 40% by weight, and the weight of the colorant is preferably 0.1 to 40% by weight with respect to the weight of the dispersion, in order to advantageously obtain the effects of the present invention. The mixing ratio when two types having different general formulas are mixed and used is not particularly limited, but is preferably 1/99 to 99/1, and particularly preferably 1/99 to 99/1.
0/90 to 90/10.

As the coloring agent used in the present invention, various dyes and pigments can be used. In the present invention, it is possible to use various colors for use in printing, for example, pigments or dyes having colors matching with yellow, magenta, cyan and black, and pigments or dyes of blue, green and red. In addition, metal powders, white pigments, fluorescent pigments and the like can be used.

The following are some examples of various pigments and dyes that can be used in the present invention. Organic pigments and dyes of azo type, phthalocyanine type, quinacridone type, anthraquinone type, indigo type, methine type and the like, or inorganic pigments. Some specific examples of these are described below.

(CI means color index) Lemon Chrome Yellow M35 (CI 77603) Medium Chrome Yellow (CI 77600) Molypdate Orange (CI 77605) Miloli Blue 671 ( CI 77510) Seikalite Blue (CI. 74200) Seikalite Rose (CI. 45160: 1) Seikalite Magenta (CI. 45170: 2) Seikalite Blue (CI. 42595: 2) Seikalite Violet B800 (CI. 42535: 2) Seika Fast Lake Red CZA665 (CI. 15585: 1) Seika Fast Red LR116 (CI. 15630: 1) Seika Fast Carmine 6B 1488 (CI. I. 15850: ) Seika First Red 8040 (CI. 15865: 1) Seika First Yellow 10GH (CI. 11710) Seika First Yellow GH (CI. 11680) Seika First Yellow 2015 (CI. 11741) Seika First Yellow A-3 (CI. 11737) Seika First Yellow 2300 (CI. 21090) Seika First Yellow 2200 (CI. 21095) Seika First Yellow 2400 (CI. 21105) Seika First Yellow 2600 (CI. I.21100) Seika First Yellow 2500 (CI.21096) Seika First Yellow 2720 (CI.21108) Seika First Orange 2900 (CI.21160) Kafast Orange 900 (CI. 21110) Seika First Orange 3044 (CI. 12075) Seika Fast Red 930 (B) (CI. 21120) Seika First Scarlet G conc (CI. 12315) Seika First Carmine 3840 (C.I. 12490) Seika Fast Carmine 3870 (C.I. 12485) Seika Fast Rubin RK-1 (C.I. 12317) Seika First Violet FR (C.I. 12322) Chromofine Blue 4920 (C. .I.74160) Chromofine Green 2GO (CI.74260) Chromofine Yellow 5910 (C.I. I. 20035) Chromofine Orange 6726 (CI not listed) Chromofine Scarlet 6750 (CI not listed) Chromofine Red 6820 (CI46500) Chromofine Violet (CI51319) Dainippon Seika Co., Ltd. Shimla First Yellow 8GTF (CI. 21105) Shimla First Yellow 4186 (CI. 11767) Shimla First Yellow 4193G (CI. 21100) Shimla First Yellow GHK-N4 (C.I. I. 21090) Shimla First Yellow GTF230T (CI not listed.) Shimla First Yellow RF (CI 21096) Shimla First Yellow 418 (C 21108) Fast Gen Super Yellow GRO (CI. 56280) Shimla Fast Pyrazolone Orange G (CI. 21110) Shimla Fast Orange V (CI. 21160) Shimla Fast Orange 4183H (CI. 11780) ) Shimla Lake Red C conc 130 (CI. 15585: 1) Shimla Neo Thor Red 2BY (CI. 15565: 1) Shimla Red 2BS (CI. 15865: 1) Fastgen Super Red 2Y (C.I. I.73905) Fast Gen Super Red 7083Y (CI. 46500) Shimla Red 3013 (CI. 15865: 2) Shimla Brilliant Carmine 6B246 (CI. 15850: 1) Fast Gens -Permagenta R (CI.73915) Fast Gen Super Violet RNS (CI.51319) Fast Gen Super Blue 6016 (CI.69800) Fast Gen Blue BSF-A (CI.74160) Fast Gen Blue TGR -L (CI. 74160) Fast Gen Green S (CI. 74260) Fast Gen Green 2YK (CI. 74265) Oriental Yellow GT (CI. 11680) manufactured by Dainippon Ink Co., Ltd. Victoria Pure Blue (CI. 42595) Lionol Red 7B4401 (CI. 15830) Lionol Red 3901 (CI. 12120) Lionol Red FB5500 (CI. 12490) Lionol Red FBK (CI. 12490) Lionol Yellow No. 7100 (CI. 21096) Lionol Yellow FGG-3 (CI. 21127) Lionol Yellow NBR (CI. 21108) Lionol Yellow 1806-G (CI. 21127) Lionol Red 2BK ( CI15865: 4) Lionol Yellow K-5G (CI.13960) Lionol Yellow K-2R (CI.13955) Lionol Yellow FGG-3 (CI.11127) Lionol Blue 7210-V (C.I. 74160) Lionol Blue SM (C.I. 74160) Lionol Blue FG-7330 (C.I. 74160) Lionol Blue SPG-8 (C.I. 74160) Lionol Blue ESP-S (CI. 74160) Lionol Blue ES (CI. 741) 0) Lionol Green B-201 (CI. 74260) Lionol Green Y-101 (CI. 74260) Lionol Green 6Y-501 (CI. 74160) Lionon Yellow GF (C .I. 70600) Lionon Yellow 3G-F (CI not listed.) Lionon Yellow RX-F (CI. 66280) Lionon Orange RF (CI. 11780) Rio Nogen Orange GR-F (C.I. 71105) Rionogen Brown RF (C.I. 12510) Rionogen Red YF (C.I. 46500) Rionogen Red 6B-F (C .. 46500) Rionogen Red GD-F (C.I. 53900) Rionogen Magenta RF (C.I. 73915) Rionogen Bio RL-F (C.I. 51319) Rionogen Blue R.F. (C.I. 69800) Rionogen Blue R3-F (C.I. 69800) Auramin (C manufactured by Toyo Ink Co., Ltd.) .I.41000) Carotene brilliant flavin (CI basic 13) Rhodamine 6GCP (CI.45160) Rhodamine B (CI.45170) Safranin OK 70: 100 (CI.50240) Erioglaucine X (CI. 42080) Fast Black HB (CI. 26150) Benzidine Yellow 4T-564D (CI. 21095) Mitsubishi Carbon Black MA-1000 Mitsubishi Carbon Black # 30, # 40, # 50 ε-type copper phthalocyanine, β-type copper phthalocyanine, brilliant carmine 6B, O Tsu Chang Red B, C. I. Pigment Red 122 and 176, Pigment Yellow 12, and dye derivatives described in JP-B-39-28884 and JP-A-1-205149.

The solvent is preferably an organic solvent, for example, methylene chloride, chloroform, trichloroethane,
Chlorinated solvents such as trichloroethylene, chlorobenzene, dichlorobenzene and carbon tetrachloride; alcoholic solvents such as furfuryl alcohol, tetrahydrofurfuryl alcohol and benzyl alcohol; ether solvents such as dioxane and tetrahydrofuran; ethylene glycol monomethyl ether; ethylene Ethylene glycol monoalkyl ethers such as glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether; diethylene glycol monoalkyl ether solvents; ethylene glycol Ethyl ether Ester solvents such as tate, diethylene glycol ethyl ether acetate and ethyl acetate (ethyl acetate); nitrogen-containing compounds such as dimethylformamide, methylpyrrolidone, nitroethane and nitrobenzene; methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, methyl Examples thereof include ketone solvents such as cyclohexanone and 4-methyl-4-methoxy-2-pentanone; dimethyl sulfoxide, toluene, and the like. One or more of these are appropriately selected and used.

The solid dispersion composition of the present invention is a fluid or semi-fluid composition containing finely divided solids in a deagglomerated state, and a dispersion of each of these solids is commonly used. It can be used for applications.
Therefore, the solid dispersion composition is useful in producing such an ink by mixing the dispersion composition with other components commonly used in the production of gravure inks for publications and newsprint inks. The dispersion composition is also useful in the production of paints by mixing conventional alkyds or other resins, etc., and in the case of producing fiber printing inks or solvent-based dyeing inks and dyes having sublimation properties. It is a disperse dye and is also useful for transfer printing. Further, it is also useful when producing inks for inkjet, color proof photosensitive materials, compositions for producing liquid crystal color filters, and the like.

Usually, when a photosensitive solution described later is added, the finely dispersed state is destroyed, that is, the particle size of the uniformly dispersed solid increases, and the solid in the dispersion may settle. The use of a compound prevents such a phenomenon,
It also has the effect of showing good compatibility with the added photosensitive solution.

[3] Photosensitive composition The photosensitive composition of the present invention comprises at least one compound selected from the compounds represented by formulas (1) and (2) and a solid. .

As the photosensitive compound used in the photosensitive composition of the present invention, a compound which is reactive to radiation and capable of causing a change in properties enough to form an image by the reaction is used. . Both positive and negative photosensitive compounds can be used.

As the negative photosensitive compound constituting the negative photosensitive composition, a diazo compound / azide compound can be used. The diazo compound refers to a compound having at least one diazo group in a molecule, and includes a chain diazo compound and an aromatic diazo compound, and the following diazo resins are preferable. The azide compound in the present invention refers to a compound having at least one N ₃ group in the molecule. The photoreceptor may be one containing one or more diazo compounds or one containing two or more azide compounds.
It may be contained in any combination of more than one kind. In the negative photosensitive composition, the content of the diazo compound and / or the azide compound is preferably 0.5 to 40% by weight, more preferably 2 to 30% by weight, based on the solid content of the photosensitive composition. .

Specifically, the following are preferred. That is, it is a diazo resin represented by a condensate of an aromatic diazonium salt with formaldehyde or acetaldehyde. Particularly preferably, a salt of a condensate of p-diazodiphenylamine with formaldehyde or acetaldehyde,
For example, a diazo resin inorganic salt which is a reaction product of hexafluoroborate, tetrafluoroborate, perchlorate or periodate with the condensate, and US Pat.
No. 00,309, the condensate and a sulfonic acid such as paratoluenesulfonic acid or a salt thereof, a phosphinic acid such as benzenephosphinic acid or a salt thereof, a hydroxyl group-containing compound such as 2,4-dihydroxybenzophenone, Examples thereof include organic salts of diazo resins which are reaction products with 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid or a salt thereof.

As another negative photosensitive compound, a photopolymerizable photosensitive composition can be used. The photopolymerizable compound used in the photopolymerizable photosensitive composition is not particularly limited, and any known photopolymerizable compound can be used.

Examples of the photopolymerizable compound include, for example,
Nos. 5-5093, 35-14719 and 44-2
No. 8727, and acrylic acid or methacrylic acid esters of polyols [for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate], methylenebis (meth) acrylamide, bis (meth) acrylamides such as ethylenebis (meth) acrylamide, and unsaturated monomers containing a urethane group, for example, di- (2'-methacryloxy) Ethyl) -2,4-tolylene diurethane,
A reaction product of a diol mono (meth) acrylate such as di- (2-acryloxyethyl) trimethylene diurethane and a diisocyanate is exemplified. The addition amount of these photopolymerizable compounds is not particularly limited, but it is preferable to add 20 to 80% by weight to the photopolymerizable photosensitive compound.

The photopolymerizable photosensitive composition may contain a photopolymerization initiator. The photopolymerization initiator is optional. Examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds and photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by Kosar. . A specific photopolymerization initiator is disclosed in British Patent No. 1,459,563, and the photopolymerization initiator disclosed in the specification can be applied to the present invention.

Specifically, for example, benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethyl Aromatic ketones such as anthraquinone, phenanthraquinone and other aromatic ketones;
Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; methyl benzoin, ethyl benzoin and other benzoins; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
-(O-chlorophenyl) -4,5- (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer,
2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer,
And U.S. Pat. No. 3,479,185;
47,569 and 2,4,5-triacrylimidazole dimer described in U.S. Pat. No. 3,784,557, but the photopolymerization initiator that can be used is not limited thereto. Absent.

As other photopolymerization initiators, thioxanthones such as 2,4-diethylthioxanthone can be used. In this case, a compound known as a photopolymerization accelerator, for example, isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, N-methyldiethanolamine, bisdiethylaminobenzophenone and the like can be used. The addition amount of these photopolymerization initiators is not particularly limited, but it is preferable to add 0.1 to 20% by weight to the photopolymerization type photosensitive composition. Further, these photopolymerizable photosensitive compositions may contain a diazo compound, a thermal polymerization inhibitor, a plasticizer, and the like. As another negative photosensitive compound, a photocrosslinkable compound can also be used. The photocrosslinkable compound is not particularly limited, and any known photocrosslinkable compound can be used. As a preferred example, a compound containing a compound having a group capable of photodimerization can be exemplified.

Examples of the compound having a photodimerizable group include compounds having structures represented by the following general formulas (3) to (10).

[0049]

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[0050]

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In the above general formulas (3) to (10), R
₁ represents an aryl group or a heterocyclic group, which has an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a nitro group, an amino group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group or an azide group. It may be. R _{2 in the} general formula (3) is a hydrogen atom or a group having 1 to 10 carbon atoms.
Wherein R ₃ is a hydrogen atom, having 1 to 10 carbon atoms.
Represents an alkyl group, an aryl group, an alkanoyl group or a cyano group. n shows the integer of 0-5.

In the general formula (8), Ar represents an aryl group, R ₄ represents a hydrogen atom, a halogen atom, and a C 1 -C 1
And 0 represents an alkyl group or a cyano group.

Examples of the compounds having the structures represented by the general formulas (3) to (10) include cinnamate and β-
Furyl acrylate, α-cyanocinnamic acid ester, p-azido cinnamate, β-styryl acrylate, α-cyano-β-styryl acrylate, p-phenylenediacrylate, p-
(2-benzoylvinyl) -cinnamic acid ester, β-naphthyl acrylate, cinnamylidenpyruvate, α-methyl-β-styryl acrylate, α-phenyl-β-styryl acrylate,
α-cyano-β-furyl acrylate and α-dimethylaminocinnamic acid ester, as well as amides, chalcones, benzylideneacetones corresponding to the above esters,
Examples include, but are not limited to, stilbazole, stilbene, α-phenylmaleimide, coumarin, pyrone, anthracene, dibenzazepine, and derivatives thereof. These compounds having photodimerizable groups can be used alone or as a mixture of two or more compounds.

As the photocrosslinkable compound, it is preferable to use a sensitizer in addition to the compound having a group capable of photodimerization. Representative examples of the sensitizer include 2,4,7-trinitro-9-fluorenone, 5-nitroacenaphthene,
p-nitrodiphenyl, p-nitroaniline, 2-nitrofluorenone, 1-nitropyrene, N-acetyl-4
-Nitro-1-naphthylamine, N-benzoyl-4-
Nitro-1-naphthylamine, Michler's ketone, N-
Butylacridone, 5-benzoylacenaphthene, 1,
8-phthaloylnaphthalene, 1,2-benzanthracene, 9,10-phenanthraquinone, chlorbenzanthrone, N-phenylthioacridone, 1,2-benzanthraquinone, N-methyl-2-benzoylmethylene -Β-naphthothiazole, 2-chlorothioxatone,
Examples include, but are not limited to, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, eosin, ellistocin, and picramide. The use of these sensitizers is not indispensable, but is used for the purpose of increasing the light use efficiency on the longer wavelength side. The photosensitive compounds used in the negative photosensitive composition can be used alone or in combination.

As the photosensitive compound constituting the positive photosensitive composition, a quinonediazide compound is used. Specifically, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5
A compound obtained by condensing any one of -sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and a compound containing a hydroxyl group and / or an amino group is preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolak resin,
Examples include resorcinol benzoaldehyde condensed resin and pyrogallol acetone condensed resin. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4'-diaminodiphenylamine, and 4,4-diaminobenzophenone. As the hydroxyl group-containing compound, an ester compound of a phenol and an aldehyde or ketone with a polycondensation resin is preferably used.

Examples of the phenols include monohydric phenols such as phenol, o-, m-, p-cresol, 3,5-xylenol, carvacrol and thymol;
Examples include dihydric phenols such as catechol, resorcin and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin.

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde and furfural. Preferred among these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol-formaldehyde resin, P-cresol-formaldehyde resin, m-cresol-formaldehyde resin, m-, p-mixed cresol-formaldehyde resin, resorcin-benzaldehyde resin, Pyrogallol / acetone resin;

As the quinonediazide compound, the following compounds described in JP-A-58-43451 can also be mentioned. That is, for example, well-known 1,2- such as 1,2-benzoquinonediazidosulfonic acid ester, 1,2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide, and 1,2-naphthoquinonediazidosulfonic acid amide. Quinonediazide compounds, specifically J. Kosar (J. Kosar)
Written by "Light Sensitive Systems"("Light
t-Sensitive Systems ") (196
5 years), John Willie and Sons (John
Wi1ey & Sons, Inc. (New York) and WSD De Fos (WS De Fo)
rest) "Photoresist" (Photoresi)
st) Volume 50, (1975), McGraw-Hill (Mc
(Grow-Hill) Co., Ltd. (New York), Nagamatsu, Inui, "Photosensitive Polymer", Kodansha (1977).

For example, 1,2-benzoquinonediazide-
4-sulfonic acid phenyl ester, 1,2-naphthoquinonediazido-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5
A condensate of 2 mol of sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone, 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-1,1'-diphenylsulfone 1 Molar condensates, 1,2-quinonediazide compounds and the like can be mentioned. In addition, Japanese Patent Publication Nos. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, and 45-27
No. 345, No. 51-13013, JP-A-48-965.
No. 75, 48-63802, 48-63803, and 1,2-quinonediazide compounds.

Of the above quinonediazide compounds, 1,2
A quinonediazide ester compound obtained by subjecting -naphthoquinonediazide-4-sulfonyl chloride to a condensation reaction with a hydroxyl group-containing compound is particularly preferred. As the quinonediazide compound, each of the above compounds may be used alone,
Also, two or more kinds may be used in combination. The addition amount of these quinonediazide compounds is preferably from 2 to 70% by weight in the photosensitive composition, more preferably from 5 to 60% by weight.

Various binders can be used in the photosensitive composition of the present invention. As the binder,
Various known polymers can be used. For details of specific binders, see US Pat.
No. 2,527. Also, for example, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer,
Vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, unvulcanized rubber, polyether, polyamide, urea resin, alkyd resin, melamine resin, gum rosin, polyterpene, coumaroindene resin, polyacrylonitrile butadiene, polyvinyl acetate, Lipophilic polymer compound having a hydroxyl group (for example, a monomer having an aliphatic hydroxyl group in a side chain, for example, a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with another copolymerizable monomer) A monomer having an aromatic hydroxyl group (for example, N-
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
Or a copolymer of p-hydroxystyrene, o-, m- or p-hydroxyphenyl methacrylate) and another copolymerizable monomer, a polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit, Natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins,
Linear polyurethane resins, phthalated resins of polyvinyl alcohol, cellulose derivatives such as cellulose acetate and cellulose acetate phthalate, epoxy resins obtained by condensing bisphenol A and epichlorohydrin, alkali-soluble resins (for example, novolak resins, vinyl resins having phenolic hydroxyl groups) Coalescence, condensation resin of polyhydric phenol and aldehyde or ketone). As the novolak resin, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin,
Co-polycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde are exemplified.

As the binder used in the photosensitive composition of the present invention, a polymer compound having a structural unit from a carboxylic acid vinyl ester monomer represented by the following general formula (A) in the molecular structure is also preferable. used.

Formula (a) R-COO-CH = CH _{2 In the} formula, R represents a substituted or unsubstituted alkyl group having 1 to 17 carbon atoms.

In the present invention, any high molecular compound having a structural unit from the vinyl carboxylate monomer represented by the above general formula (A) in the molecular structure can be used. You may. As the carboxylic acid vinyl ester monomer represented by the general formula (a), the following exemplified carboxylic acid vinyl ester monomers are preferable.

1 Vinyl acetate CH ₃ COOCH ＝ CH ₂ 2 Vinyl propionate CH ₃ CH ₂ COOCH ＝ CH ₂ 3 Vinyl butyrate CH ₃ (CH ₂ ) ₂ COOCH ＝ CH ₂ 4 Vinyl pivalate (CH ₃ ) ₃ CCOOCH ＝ CH ₂ 5 vinyl caproate _{CH 3 (CH 2) 4 COOCH} = CH 2 6 caprylic vinyl _{CH 3 (CH 2) 6 COOCH} = CH 2 7 capric acid vinyl _{CH 3 (CH 2) 8 COOCH} = CH 2 8 vinyl laurate CH ₃ (CH ₂ ) ₁₀ COOCHＣＨCH ₂ 9 Vinyl myristate CH ₃ (CH ₂ ) ₁₂ COOCH ＝ CH ₂ 10 Vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COOCH ＝ CH ₂ 11 Vinyl stearate CH ₃ (CH ₂ ) ₁₆ COOCH = CH ₂ 12 vinyl versatate

[0068]

Embedded image

In the formula, R ¹ and R ² represent an alkyl group, and the sum of the carbon atoms is 7. The alkyl group represented by R ¹ and R ² may have a substituent, for example, a vinyl ester of a substituted carboxylic acid.

The polymer compound may be a polymer obtained by polymerizing the carboxylic acid vinyl ester monomer represented by the general formula (A) alone, or two or more kinds of the carboxylic acid vinyl ester represented by the general formula (A). Even when a polymer obtained by copolymerizing a monomer is used in combination, or when one or more vinyl carboxylate monomers represented by the general formula (A) and another monomer copolymerizable therewith are copolymerized at an arbitrary component ratio. Polymer.

As other monomers to be copolymerized with the carboxylic acid vinyl ester monomer represented by the general formula (A), for example, the following may be mentioned.

(1) Ethylene unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (2) styrene, α-methylstyrene, p-
Styrenes such as methylstyrene and p-chlorostyrene,
(3) acrylic acids such as acrylic acid and methacrylic acid;
(4) unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride; (5) diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-fumarate. Diesters of unsaturated dicarboxylic acids such as ethylhexyl, (6)
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, dodecyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, α
Α-methylene aliphatic monocarboxylic acid esters such as methyl chloroacrylate, methyl methacrylate and ethyl methacrylate; (7) nitriles such as acrylonitrile and methacrylonitrile; (8) amides such as acrylamide; Anilides such as acrylic anilide, p-chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide; (10) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether; Vinyl chloride, vinylidene chloride, vinylidene cyanide, (12) 1-methyl-1-
Methoxyethylene, 1,1-dimethoxyethylene, 1,
Ethylene derivatives such as 2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, (13) N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene And vinyl monomers such as N-vinyl compounds such as N-vinylpyrrolidone. Particularly preferred as the above-mentioned polymer compound is a compound having a structural unit derived from vinyl acetate in the molecular structure. Among them, 40 units of vinyl acetate polymerized units
-95% by weight, and the number average molecular weight (Mn) is 1,000
~ 100,000, weight average molecular weight (Mw) of 5,000
Those having 0 to 500,000 are preferred. Further preferred polymer compounds are vinyl acetate and vinyl esters of carboxylic acids having a longer chain than that of acetic acid, preferably having 4 to 17 carbon atoms,
Particularly preferred is a copolymer containing vinyl versatate,
In particular, the number average molecular weight (Mn) is 2,000 to 60,00
0, weight average molecular weight (Mw) of 10,000 to 150,
000 is preferred.

In the copolymer, vinyl acetate is 40 to
Particularly preferred is 95% by weight, and particularly preferred is 5 to 50% by weight of the vinyl ester of a carboxylic acid having a longer chain than acetic acid. When obtaining the above-mentioned polymer compound, another monomer can be used as a comonomer. As the comonomers, any comonomers can be used, and these comonomers can be arbitrarily selected from, for example, the monomers exemplified above.

The polymer compounds usable in the present invention are listed below by showing their monomer components. However, needless to say, the polymer compound that can be used in the present invention is not limited to the polymer compounds exemplified below.

1 vinyl acetate-ethylene 2 vinyl acetate-styrene 3 vinyl acetate-crotonic acid 4 vinyl acetate-maleic acid 5 vinyl acetate-2-ethylhexyl acrylate 6 vinyl acetate-di-2-ethylhexyl maleate 7 vinyl acetate-methyl vinyl ether Reference Signs List 8 vinyl acetate-vinyl chloride 9 vinyl acetate-N-vinylpyrrolidone 10 vinyl acetate-vinyl propionate 11 vinyl acetate-vinyl pivalate 12 vinyl acetate-vinyl versatate 13 vinyl acetate-vinyl laurate 14 vinyl acetate-vinyl stearate 15 Vinyl acetate-vinyl versatate-ethylene 16 Vinyl acetate-vinyl versatate-2-ethylhexyl acrylate 17 Vinyl acetate-vinyl versatate-vinyl laurate 18 Vinyl acetate-bar Vinyl ticate-crotonic acid 19 Vinyl propionate-vinyl versatate 20 Vinyl propionate-vinyl versatate-crotonic acid 21 Pivalic acid-vinyl stearate-maleic acid The photosensitive composition of the present invention has been described above. In addition to each material, the following additives can be further used as needed.

For example, alkyl ethers (eg, ethylcellulose, methylcellulose), fluorinated surfactants, and nonionic surfactants (eg, Pluronic L-64 (Asahi Denka Co., Ltd.)
Plasticizer (for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), and a sensitizing agent for improving the lipophilicity of the image area (for example, JP-A-55 / 55) No. 527, half-esterified product of styrene-maleic anhydride copolymer with alcohol, p-te
rt-butylphenol formaldehyde resin or pn
-Octylphenol formaldehyde resins, or resins in which these resins are partially esterified with quinonediazide compounds, etc., stabilizers [for example, phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, Naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.)]
Examples include development accelerators (eg, higher alcohols, acid anhydrides, etc.), and inorganic powders (colloidal silica, calcium carbonate, titanium oxide, etc.) for imparting shape retention. Also, the photosensitive composition of the present invention includes USP 3,37
Diatom oxides, aluminum oxide, tertiary butyl benzoic acid, which are found in U.S. Pat.
Organic dye derivatives having a polar group, for example, Japanese Patent Publication No. 41-2
Compounds obtained by introducing a substituent such as a sulfone group, a sulfonamide group, an aminomethyl group and a phthalimidomethyl group into a side chain using an organic pigment represented by No. 466 and US Pat. Kaisho 56
-167761, 56-167762 and 56
It is preferable to add a compound described in -161827 or the like. The amount of these additives varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content of the photosensitive composition.

The photosensitive composition of the present invention comprises the above-mentioned quinonediazide compound, a photopolymerizable and / or photocrosslinkable compound and a photosensitive compound such as a diazo compound and / or an azide compound, and a binder (binder) used together therewith. Each of the additives can be produced by dissolving each of the additives using the above-described organic solvent to obtain a photosensitive solution, and then adding the resulting solution to the above-described colorant dispersion. When the photosensitive composition of the present invention is prepared by adding a photosensitive solution to a colorant dispersion, the compound of the present invention is preferably added at the time of preparing the colorant dispersion. In addition, the compound of the present invention, the colorant, the photosensitive compound, the binder, and the additive can be simultaneously dissolved and dispersed to produce the compound. However, the present invention is not limited to these.

[4] Photosensitive Material for Color Proof When the photosensitive composition of the present invention is used to form, for example, a photosensitive material for color proof (also referred to as an image forming material),
This can be achieved by using the above photosensitive composition as a coating liquid and applying the coating liquid on a support to provide a photosensitive layer. As a coating method used for coating the photosensitive composition on the surface of the support, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, electrostatic air spray coating, roll coating , Blade coating and curtain coating are used.

The thickness of the photosensitive layer can be determined by a method known to those skilled in the art according to the target optical density, the type of colorant used in the photosensitive layer and the content thereof. The smaller the layer thickness, the higher the resolving power and good image quality can be obtained. From the above viewpoint, the film thickness is usually 0.1 to 5 g / m ^{2 on a} dry basis.
The film thickness obtained in the range is adopted.

The support for constituting the image forming material includes:
It may consist of any material. When back exposure is required, a transparent support is generally used. As the support, a polyester film, particularly a polyethylene terephthalate film, particularly a biaxially stretched polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat. In addition, an acetate film, a polyvinyl chloride film, a polystyrene film, a polypropylene film, a polycarbonate film, and a polyimide film can also be preferably used. It is preferable that the surface of these supports is subjected to an appropriate subbing treatment in order to improve the coating properties of the photosensitive layer and the adhesiveness of the photosensitive layer. Further, an antihalation layer containing a dye or a pigment may be provided on the front or back surface of these supports for the purpose of preventing halation or the like. The surface of the support opposite to the side on which the photosensitive layer is provided is preferably matted for the purpose of improving the slipperiness of the recording material and the adhesion to the original during exposure. It is preferable to form a back coat layer on the surface of the support opposite to the photosensitive layer. The back coat layer can be formed of a silicone resin or the like.

In the present invention, a heat-softening release layer is preferably provided on the surface of the support. Here, the thermal softening release layer is a general term for a layer functioning as a thermal softening layer and / or a layer functioning as a releasing layer, and is used when a colored image formed on a support is transferred to a material to be transferred. In addition, those provided so that the colored image is easily peeled off from the support are collectively referred to. For example, a material that facilitates the peeling by softening by heat or an effect that facilitates the peeling and deforms following the irregularities of the transfer surface of the image receptor and pushes the transferred layer into the irregularities of the image receptor (Referred to as a heat-softening layer) and a layer formed by subjecting the surface of the support to a release treatment with a turbulent substance (referred to as a release treatment layer).

The image forming material can be used in the form of transferring an image to a material to be transferred. At this time, in order to perform efficient transfer onto the material to be transferred and to facilitate peeling of the support after the image is transferred, that is, the releasability between the support and the photosensitive layer formed on the image forming material. It is preferable that the release layer is provided on the surface of the support in order to increase the surface roughness.

For example, in the practice of the present invention, a release layer is provided on a support by a thermal softening layer (preferably a release treatment layer is preferably formed thereon), and a colored photosensitive layer is formed thereon. The structure to be formed can be taken. Such a thermal softening layer can be composed of, for example, a vinyl acetate-ethylene copolymer.

The release treatment layer is made of, for example, silicone resin, fluorine resin, 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, It can be formed from a polyamide resin such as wax, nylon and copolymerized nylon. Further, a melamine resin or a polyacrylate urethane resin to which a silicone resin or a fluorine resin is added can also be used. or,
Polypropylene film and polyethylene film, etc. show good releasability even without special release treatment, so it is preferable that the thickness is smaller than the thickness of the support, and a polypropylene layer or a polyethylene layer is provided as a release layer. be able to. Examples of a method for providing a polypropylene layer or a polyethylene layer on a support include a so-called dry lamination method, a hot melt lamination method, an extrusion lamination method, and a coextrusion method. The thickness of the release treatment layer is suitably in the range of 0.01 to 30 μm, and particularly preferably in the range of 0.1 to 5 μm.

The thermal softening layer has the property of softening at the temperature during thermal transfer, and can be formed of a thermoplastic resin. As a thermoplastic resin, the softening point is −30 ° C.
Those at 200 ° C. are preferred. The softening point temperature here is
It is the value indicated by the VICAT softening point or the ring and ball method. In the present invention, specifically, the following, for example, polyethylene,
Polyolefins such as polypropylene; ethylene and vinyl acetate, ethylene and acrylic acid esters, ethylene and acrylic acid such as ethylene copolymers; polyvinyl chloride, vinyl chloride and vinyl acetate copolymers such as vinyl acetate; polyvinylidene chloride; vinylidene chloride Copolymer; polystyrene, styrene and styrene copolymer such as maleic anhydride; polyacrylate, polyester resin; polyurethane resin; acrylate and vinyl acetate copolymer such as vinyl acetate; polymethacrylate; Methyl methacrylate and vinyl acetate, methacrylate copolymers such as methyl methacrylate and acrylic acid; polyvinyl acetate, vinyl acetate copolymer; vinyl butyral resin; nylon, nylon copolymer, N-alkoxymethylation Na Ron such polyamide resins; synthetic rubber, petroleum resin, chlorinated rubber, polyethylene glycol,
Preferred resins include polyvinyl alcohol hydrozine phthalate, cellulose derivatives, cellulose acetate phthalate, cellulose acetate succinate, shellac, and wax.

The heat softening layer can be provided on the support by using a known method. For example, a method in which a solution or emulsion of the resin for forming a thermal softening layer in an organic solvent, a latex of hydrogen, or an emulsion thereof is applied to a support. The thickness of the heat-softening layer is preferably in the range of 1 to 50 µm, particularly preferably in the range of 5 to 30 µm.

The above-mentioned release treatment layer can be provided on the heat-softening layer. This method includes, for example, dissolving the above-mentioned resin for forming the release treatment layer in an organic solvent, or emulsifying the solution to form a heat-softening layer. And a method of laminating a polypropylene film or a polyethylene film on the heat softening layer.

Further, a protective layer may be formed on the image forming material. As the protective layer, any of known protective layers can be used, but those which dissolve or disperse in a developing solution during development are preferable. Otherwise, it is peeled off after image exposure. Specific examples of the material for forming the protective layer include polyvinyl alcohol and celluloses. The gas permeability of the protective layer is appropriately selected according to the type of the photosensitive compound used. For example, when a photosensitive compound that generates a gas at the time of exposure such as o-quinonediazide is used, it is preferable to use a material that provides a protective layer with good gas permeability in order to dissipate the generated gas. When a photosensitive compound whose image formation is inhibited by oxygen in the air, such as a polymerization type photosensitive compound, is used, it is preferable to use a material that provides a protective layer having low gas permeability.

The thickness of the protective layer is optional, but is 0.01 to 5 μm in consideration of the effect of the protective layer, the influence of the developing solution, and the like.
It is preferably about 0.03 to 1 μm. The protective layer can be formed using a film sheet that is peeled off or removed before use or during use. Examples of these film sheets include a polyethylene film, a polypropylene film, and a polyethylene terephthalate film. The preferred thickness of the film varies depending on the material of the film used, but is preferably about 5 to 100 μm from the viewpoint of workability and economy.

To form a colored image using the color proofing light-sensitive material of the present invention, the photosensitive material is exposed through a transparent original having a line image, a halftone dot image, and the like, and then developed with a developing solution. Thus, a negative or positive relief image is obtained. Thereafter, the formed relief image is transferred to a material to be transferred to obtain a colored image. The light source of the active light suitable for exposure includes a carbon arc lamp, a mercury lamp, a xenon lamp, a chemical lamp, a metal halide lamp, a strobe, and the like.

When embodied as a multicolor image forming method,
The basic method includes the following method. That is, a first image having a colored image forming layer for a first color on a support
A first color image is formed on the color image forming material, and at least the color image is transferred to a material to be transferred, and the support is peeled off. Further, after forming the second color image on the second color image forming material, the second color registration mark image formed along with the second color image is
The second color image is transferred onto the first color image while registering with the first color register image on the transfer material, and the support is peeled off to obtain an image in which the two colors are aligned. Similarly, the colored images of the third color and the fourth color are transferred to the material to be transferred to obtain a multicolor image. In some cases, the multicolor image is indirectly transferred onto another transfer material to obtain a multicolor image. This type of method is disclosed in Japanese Patent Laid-Open No. 47-41830.
Nos. 59-97140, 60-28649 and U.S. Pat. No. 3,775,113.

Examples of the material to be transferred include fibrous base materials such as paper, polyethylene-coated paper, polypropylene-coated paper and cloth; sheets and foils of metals such as aluminum, copper, magnesium and zinc; poly (alkyl methacrylate); For example, poly (methyl methacrylate), polyester film base such as poly (ethylene terephthalate), poly (vinyl acetal) polyamide such as nylon, cellulose ester film base such as cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate Such synthetic polymer materials as mentioned above can be used.

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. For example, an alkaline aqueous developer is preferably used. Alkali agents used in this developer (including replenisher) include sodium silicate, potassium silicate, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and tertiary phosphate. Potassium, dibasic potassium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate,
Useful are inorganic alkali agents such as potassium carbonate, ammonium carbonate and the like, organic alkali agents such as mono-, di- or triethanolamine and tetraalkylammonium hydroxide, and organic ammonium silicate. Of these, silicates are preferred, and alkali metal silicates are most preferred. The content of the alkali agent in the developer is 0.
It is preferably used in the range of from 0.5 to 20% by weight, more preferably from 0.1 to 10% by weight.

Additives such as an organic solvent, a water-soluble reducing agent, a surfactant and a chelating agent can be added to the developer. Examples of such organic solvents include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate,
Carboxylic acid esters such as ethylene glycol monobutyl acetate, butyl lactate and butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol monobutyl ether, ethylene glycol benzyl ether;
Alcohols such as ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, and methyl amyl alcohol; glycols such as ethylene glycol and propylene glycol; alkyl-substituted aromatic hydrocarbons such as xylene; Examples thereof include halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochloroben. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether, ethylene glycol benzyl ether and benzyl alcohol, and propylene glycol are particularly preferred.

The following additives can be added to the developer to further enhance the developing performance. For example, NaCl, KCl, KBr described in JP-A-58-75152
And EDT described in JP-A-58-190952.
A, chelating agents such as NTA, JP-A-59-121336
Such as [Co (NH ₃ ) ₆ ] Cl ₃ described in US Pat.
Highly amphoteric polymers such as cationic polymers such as quaternary methyl chloride of p-dimethylaminomethylpolystyrene described in JP-A-5-95946 and copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528. Molecular electrolyte, JP-A-5
Reducing inorganic salts described in JP-A-7-192552;
No. 59444, an inorganic lithium compound such as lithium chloride; Japanese Patent Publication No. 50-34442; an organic lithium compound such as lithium benzoate; Japanese Patent Publication No. 59-75255; an organometallic surfactant containing Si, Ti, etc .; Kaisho 5
No. 9-84241, organic alcohol compounds, higher alcohol sulfates, aliphatic alcohol phosphates, alkylaryl sulfonates, sulfonates of dibasic aliphatic esters, formaldehyde condensates of alkylnaphthalene sulfonates, Anionic surfactants such as alkyl amide sulfonates are exemplified.

[0096]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In addition, "part"
Represents "parts by weight".

Example 1 A mixture shown in Table 1 below was added to a dispersion vessel equipped with a water-cooled jacket, and glass beads having a diameter of 2 mm were added.
Dispersion was performed for 4 hours at 2000 rpm with a stirring disk attached, to produce solid dispersion compositions 1 to 8. Hereinafter, these are referred to as pigment dispersions 1 to 8.

[0098]

[Table 1]

*: Carbon black MA-100 manufactured by Mitsubishi Chemical Corporation The pigment dispersions 1 to 8 obtained were allowed to stand for 1 day, and then sedimentation of the pigment was confirmed. Next, the particle diameters of the pigments of the pigment dispersions 1 to 8 were determined by Series 703 manufactured by MALVERN.
2 Measured with Multi-8 Correlator, further placed the pigment dispersions 1 to 8 in a sealed container and allowed to stand, and the particle size of each pigment after 1, 2 and 3 months and after 6 months Was measured. The results are shown below.

[0100]

[Table 2]

As is evident from the results obtained, the pigment dispersions 1 to 8 of the present invention have a small variation in particle size, and have good dispersibility and dispersion stability.

Example 2 A mixture shown in Table 3 below was added to a dispersion vessel equipped with a water-cooled jacket, and glass beads having a diameter of 1 mm were added.
Dispersion was performed at 2000 rpm for 5 hours with a stirring disk attached, to prepare pigment dispersions 1 to 5.

[0103]

[Table 3]

*: Seika First Yellow H7055 manufactured by Dainichi Seika Kogyo Co., Ltd.

[0105]

Embedded image

After leaving the obtained pigment dispersions 1 to 5 for one day, sedimentation of the pigment was confirmed. Next, the particle diameters of the pigments of the pigment dispersions 1 to 5 were measured by the measuring instrument used in Example 1. Further, the pigment dispersions 1 to 5 were placed in a closed container and allowed to stand,
The particle size of each pigment was measured after a lapse of a few months and after a lapse of 6 months. The results are shown below.

[0107]

[Table 4]

As is clear from the obtained results, it is understood that the pigment dispersions 1 to 5 of the present invention have good dispersibility and dispersion stability.

Example 3 Pigment dispersions 1 to 4 were prepared, and were allowed to stand for 3 months, and were checked for sedimentation after settling. Table 5 shows the results.

[0110]

[Table 5]

The pigment dispersion containing the compound of the present invention is
It can be seen that there was no sedimentation of the pigment even after standing for 3 months in a sealed state, and the aging was excellent.

Example 4 The following photosensitive solution 1 was prepared.

QD-1 1.7 parts Vinyl acetate-vinyl versatate copolymer (80:20 parts by weight) 50 wt% MeOH solution of copolymer (Mw = 60000) 11.5 parts Vinyl acetate-vinyl versatate- Crotonic acid (79: 20: 1 parts by weight) Copolymer (Mw = 60000) 50 wt% MeOH solution 10 parts Methyl ethyl ketone 68 parts

[0114]

Embedded image

X: Y = 1: 1 Mw of the resin before the reaction with Q = 500 Next, 4.5 parts of the pigment dispersion 3 prepared in Example 1 was collected, and 4.5 parts of methyl ethyl ketone was stirred. Was added, and after confirming that the liquid was sufficiently uniform, 91 parts of the photosensitive liquid 1 obtained as described above was charged with stirring to prepare a photosensitive composition 1. Further, a photosensitive composition 2 was prepared in the same manner as in Example 1 except that the pigment dispersion 7 prepared in Example 1 was used, and the particle diameters of the pigments of the photosensitive compositions 1 and 2 were set in the same manner as in Example 1. It was 1
It was 55 nm and 170 nm, and there was no significant change in the dispersed state as compared with the case where only the pigment was dispersed.

Example 5 The following photosensitive solution 2 was prepared.

QD-1 2.0 parts Vinyl acetate-vinyl versatate copolymer (80:20 parts by weight) 50 wt% MeOH solution of copolymer (Mw = 60000) 11.5 parts Vinyl acetate-vinyl versatate- Crotonic acid (79: 20: 1 parts by weight) 50 wt% MeOH solution of copolymer (Mw = 60000) 12 parts Methyl ethyl ketone 65.5 parts 4.5 parts of pigment dispersion 1 prepared in Example 1 was collected,
While stirring, 4.5 parts of methyl ethyl ketone were added.
After confirming that this solution was sufficiently uniform, 91 parts of the above-mentioned photosensitive solution 2 was added with stirring, and the photosensitive composition 3 was added.
Was prepared. Next, the same operation was performed except that the above-mentioned pigment dispersion liquid 1 was changed to the pigment dispersion liquids 2 to 7 of Example 1, and photosensitive compositions 4 to 9 were produced. In addition, the obtained photosensitive composition 3
To 9 are coating liquids 1 to 7. The coating liquid 3 was the same as the coating liquid 3 except that the compound of the present invention in the pigment dispersion liquid 3 prepared in Example 1 was changed to the compound described in Example 11 of JP-A-46-7294 synthesized according to the following formulation. In the same manner, a coating liquid 8 was prepared.

JP-A-46-7294, Example 11 1.5 parts of 4,4'-azobis-4-cyanopentanoyl chloride was added to 208 parts of refluxing benzene, and the mixture was further added with 90 parts.
Parts of vinyl versatate monomer under nitrogen atmosphere
Added over time. The solution was then refluxed for a further 5 hours and then cooled. This was added to a solution of 10 parts of triethylenetetramine dissolved in 40 parts of anhydrous benzene. The solution was then poured into methanol to precipitate the resulting polymer, which was crushed out and dried at 60 ° C. in a vacuum oven.

<Preparation of Support> An ethylene-vinyl acetate copolymer (EVAFL, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) was placed on a polyethylene terephthalate film having a thickness of 75 μm.
EXP-1405: vinyl acetate content 14 wt%, V
(ICAT softening point: 68 ° C.) was applied by extrusion lamination to a thickness of 30 μm to prepare a support.

<Preparation of Photosensitive Material for Proof> Coating solutions 1 to 8 were applied to the obtained support using a wire bar so that the dry coating amount was 1.8 g / m ^2, and dried to obtain a proof. Photosensitive materials 1 to 8 were prepared.

<Measurement of Developability> The obtained photographic material for proof was used in an Akira room printer (Pin manufactured by Dainippon Screen Co., Ltd.).
-647-GA). The amount of exposure was such that a step tablet for sensitivity measurement (No. 2, manufactured by Eastman Kodak Co., Ltd., gray scale of 21 steps at a density of 0.15 each) was tightly attached to the photographic material for proofing and exposed with the above printer. And then Konica Exc
Elart processor (EX900 manufactured by Konica Corporation)
L) was used to determine that 3.0 steps of the above-mentioned step tablet were completely clear when developed with Konica Excelart Developer ED (4-fold dilution) at 32 ° C. for 35 seconds.

Then, when the residual carbon black on the support of the proofing light-sensitive material after development was observed, the proofing light-sensitive material 8 was almost completely black and carbon black remained undeveloped. The photosensitive materials 1 to 7 were almost developed, and the amount of residual carbon black on the support was slight.

Further, the light-sensitive materials for proofing 1 to 8 were
Exposure was performed in the same manner as described above for each of the five images in a size of mx 40 cm. These are Konica Excelart Processor E
Konica Excelart Developer ED using X900L
After developing at 32 ° C. for 35 seconds (4 times dilution), Konica Excelart transfer film (EP-1Y (A1 size) manufactured by Konica Corporation) was immediately subjected to development processing under the same conditions in an unexposed state. The developed transfer film is subjected to a drum temperature of 70 using the Konica Excelart processor.
C., the pressure roller temperature was 110.degree. C., and the transfer time was 60 seconds, and the image was transferred to Tokishi Art Paper (Mitsubishi Paper Corp.). When the development processing is performed immediately after developing the proofing photosensitive material 8,
The transfer image on the art paper was stained by carbon black, but immediately after the proofing photosensitive materials 1 to 7 were developed, no stain was seen on the transfer image.

Example 6 The following photosensitive solution 3 was prepared.

20 g of Regal 400R manufactured by Cabot Corp. Exemplified Compound (1) -3 4 g Copper phthalocyanine disulfonic acid 1 g Michler's ketone 0.4 g Benzophenone 2.5 g Pentaerythritol tetraacrylate 60 g Vinyl acetate-vinyl versatate copolymer (copolymerization ratio = 80) : 20 (weight) Mw = 60000) 50% methyl alcohol solution 140 g 50% methyl vinyl acetate-vinyl versatate-vinyl stearate copolymer (copolymerization ratio = 80: 15: 5 (weight) Mw = 60000) 12 g of alcohol solution 765 g of methyl ethyl ketone 240 parts of the obtained photosensitive solution 3 was collected and put together with 360 parts of glass beads 1 mm in diameter into a dispersion vessel equipped with a water-cooled jacket, and a stirring disk was attached.
The dispersion was carried out at 0 rpm for 4 hours to prepare a coating liquid 9.

<Preparation of Proof Photosensitive Material> The coating solution 9 was applied to the support prepared in Example 5 using a wire bar so that the dry coating amount was 2 g / m ^2, and dried. A polyethylene terephthalate film having a thickness of 15 μm was laminated and applied on the photosensitive layer thus prepared to form a protective layer. Thus, a proofing photosensitive material 9 was produced.

<Evaluation of Developability> After the protective layer of the obtained proofing photosensitive material 9 was removed, the above Konica Excel was removed.
The photosensitive layer was developed and removed by immersing in an ED developer (diluted 4-fold) at 32 ° C. for 30 seconds. As a result, no residual carbon black was found on the support.

Example 7 A proofing light-sensitive material 10 was prepared in the same manner as in Example 6 except that the exemplified compound of Example 6 was changed to (2) -2, and the developability was evaluated in the same manner as in Example 6. No residual carbon black was found on the support, and the film had excellent developability.

[0129]

EFFECT OF THE INVENTION By using the novel compound of the present invention, which has good solid dispersibility and can stably maintain a finely dispersed state for a long period of time, it has excellent solid dispersibility and dispersion stability. In addition, even when a target composition is prepared by adding various materials later, a solid dispersion composition is obtained which has no sedimentation, is compatible with a wide range of materials, and maintains a finely dispersed state. This is a remarkably excellent effect. Further, when used as a coating solution, a photosensitive composition having high sensitivity and excellent developability is obtained, and is particularly applicable to a color proof for color proofing in color printing.

Claims (7)

[Claims] 1. A dispersion aid represented by the following general formula (1). Embedded image (R ₁ , R ₂ , R ₇ , and R ₈ each represent a hydrogen atom, and have 1 to 30 carbon atoms.
Which may have a substituent a straight chain or branched chain alkyl group, which may have a substituent the alicyclic hydrocarbon group, an aromatic hydrocarbon group and heterocyclic group, R ₃ To R ₆ represent the following structural formulas, wherein R _{9 to} R ₁₂ have the same meanings as R ₁ , n represents an integer of 0 or more, and m represents an integer of 1 or more. ) 2. A dispersing agent represented by the following general formula (2). Embedded image (A is a linear or branched alkyl group having at least three hydroxyl groups, which may have a substituent, or an alicyclic hydrocarbon group or an aromatic hydrocarbon, each of which may have a substituent. R _{13 to} R ₂₁ each represent a hydrogen atom, a linear or branched alkyl group which may have a substituent having 1 to 30 carbon atoms, Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have, x, y, and z are each an integer of 1 or more, and an integer whose sum is 5 or more. Represents.) 3. A solid dispersion composition comprising at least one compound selected from the compounds represented by the general formulas (1) and (2). 4. The solid dispersion composition according to claim 3, wherein the solid is a colorant. 5. The solid dispersion composition according to claim 4, wherein said colorant is a pigment or a dye. 6. A photosensitive composition comprising at least one compound selected from the compounds represented by formulas (1) and (2) and a solid. 7. A light-sensitive material for color proof, wherein the light-sensitive composition according to claim 6 is used.