JPH03163550A - Image forming method - Google Patents

Abstract

PURPOSE:To solve hygienic problems related to toxicity, foul odors, etc., at the time of work and safety problems related to a fire, explosion of gas, etc., to prevent bubbling and to control environmental pollution due to a waste soln. by imagewise exposing a photosensitive layer contg. specified co-condensed diazo resin and developing the exposed layer with an aq. alkaline developing soln. not practically contg. an org. solvent. CONSTITUTION:A photosensitive layer contg. co-condensed diazo resin having structural units represented by formulae I, II is imagewise-exposed and developed with an aq. alkali developing soln. not practically contg. an org. solvent. In the formulae I, II, each of R<1>-R<3> is H, alkyl, etc., each of R<4> and R<5> is H, phenyl, etc., X is PF6 or BF4, Y is -NH-, -S-, etc., and Z is phenylene or naphthylene having at least one group such as a sulfonic acid or sulfinate group as a substituent or further having other substituent. Hygienic problems related to toxicity, foul odors, etc., at the time of work and safety problems related to a fire, explosion of gas, etc., are solved, environmental pollution due to a waste soln. is controlled and cost can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image form or method suitably used for manufacturing lithographic printing plates, IC circuits, and photomasks.

[Conventional technology]

Generally, photosensitive printing plates are produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, polymerizing or crosslinking the irradiated areas, and applying a developer. Insolubilize and elute the non-irradiated areas into a developer, making each area an image area that repels water and accepts oil-based ink, and a non-image area that accepts water and repels oil-based ink. It is obtained by

As the photosensitive composition in this case, diazo resins such as a condensate of p-diazodiphenylamine and formaldehyde have been widely used.

On the other hand, when developing photosensitive lithographic printing plates using these diazo resins after exposure, the aqueous alkaline developer composition used is, for example, benzyl alcohol as disclosed in JP-A No. 51-77401. , Developing solution composition consisting of anionic surfactant, alkaline agent and water, JP-A-53
A developer composition consisting of an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite, described in Japanese Patent Application Laid-Open No. 15535-15535.
Examples include a developer composition containing an organic solvent, an alkaline agent, and water whose solubility in water is 10% by weight or less at room temperature, as described in No. 5.

All of these contain organic substances such as organic solvents and surfactants in their developer compositions. However, organic solvents have many drawbacks, such as being generally toxic and odorous, and pose a risk of fire, and are subject to BOD regulations even in waste liquid, and are also expensive.

Examples of developer compositions substantially free of these organic solvents include the developer composition described in JP-A-59-84241. However, these developer solutions are used when developing positive-working photosensitive lithographic printing plates containing an 0-naphthoquinone diazide compound as a photosensitive compound.
When a photosensitive lithographic printing plate using the above-mentioned diazo resin is developed using a developer composition that does not substantially contain a solvent, the diazo resin is essentially not alkali-soluble. However, there were problems in that proper developability could not be obtained, such as the inability to develop without leaving a residual film and yellowing of unexposed areas.

Note that "substantially free of organic solvent" means that it does not contain organic solvent to the extent that it causes inconvenience in terms of environmental health, safety, workability, etc., and in the present invention, This means that the proportion of the substance in the compound is less than 1% by weight, preferably 0% by weight.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to develop a photosensitive composition using a diazo resin having improved solubility in an alkaline aqueous solution as a photosensitive material with an aqueous alkaline developer containing substantially no organic solvent after image exposure. , the image forming method does not have any hygiene problems such as toxicity or odor during work, safety problems such as fire or gas explosion, workability problems such as generation of bubbles, or pollution problems due to waste liquid. , and to provide a low-cost image format or method.

[Means to solve the problem]

The above object of the present invention is achieved by the following general formulas (1) and (II) (wherein Rl, R2 and R3 are each a hydrogen atom, an alkyl group or an alkoxy group, and R4 and RS are each a hydrogen atom, an alkyl group or Phenyl group, X is PF. or BF4
, Y is 1NH- -S- or 101Z has at least one group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group as a substituent, and After imagewise exposure of a photosensitive layer containing a co-condensed diazo resin having a structural unit represented by a phenylene group or a naphthylene group with or without a substituent, an aqueous alkaline developer containing substantially no organic solvent is applied. This is achieved by an image form or method characterized by development.

The present invention will be specifically explained below.

The diazo resin of the present invention has the general formulas (I) and (II)
) has a structural unit represented by the general formula (III) described below.
It is obtained by co-condensation of an aromatic compound represented by and [■] and an active carbonyl compound.

One aromatic diazo compound is represented by the following general formula (III): R3 (wherein R', R'', R'', X and Y are 2 (1)
is synonymous with Examples of R'sR'' and R'' include a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, a methoxy group,
Examples include alkoxy groups such as ethoxy, preferably a hydrogen atom or a methoxy group, and particularly preferred is a hydrogen atom. Among the groups represented by Y, 1NH1 is preferred) Specific examples of aromatic diazo compounds used in the present invention include 4-diazo 4'-methoxydiphenylamine hexafluorophosphate , 4-diazo 4'-monoethoxydiphenylamine hexafluoride phosphate, 4-diazo 41-proboxydiphenylamine tetrafluoroborate, 4-diazo 3-methoxydiphenylamine hexafluoride Examples include phosphate, 4-diazo-3-methoxydiphenylamine/tetrafluoroborate, 4-diazodiphenylagon/hexafluorophosphate, and the like. Among these, preferred aromatic diazo compounds include 4-diazo 4'-methoxydif, enylamine salt, 4-diazo 4'-ethoxydiphenylamine salt, 4-diazo 3-methoxydiphenylamone salt, and 4-diazodiphenylamine salt. can be mentioned.

The other aromatic compound is represented by the following general formula (IV): Z'...(IV) (wherein, Z' is a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group). It refers to substituted benzene or substituted naphthalene having at least one substituent/group selected from the group consisting of bases and with or without other substituents.Preferably, benzene substituted with a sulfonic acid group or a sulfonic acid group. Examples of other substituents in Z in the general formula (n) and in the general formula (IV) include amino groups, carboxyl groups, and halogens such as chlorine.

Specific examples of such aromatic compounds utilized in the present invention include benzenesulfonic acid, sodium benzenesulfonate,
Disodium m-benzenedisulfonic acid, p-toluenesulfonic acid, sodium p-toluenesulfonic acid, p-toluenesulfinic acid, sodium p-toluenesulfinate, sodium benzenesulfinate, aniline-2-sulfonic acid, 4
-Amino-toluenesulfonic acid, 4-amino-
Sodium toluenesulfonic acid, 2,5-diaξnobenzenesulfonic acid, ■-naphthalenesulfonic acid, 1-amino-
2-Naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 7-amino-1,3-naphthalene disulfonic acid, 2-amino-1,5-naphthalene disulfonic acid, 4-amino ■-naphthalenesulfonic acid sodium, 5-amino Examples include sodium 1-naphthalenesulfonate, sodium 6-amino-1-naphthalenesulfonate, sodium 5-sulfoisophthalate, 2-sulfobenzoic acid, and p-chlorobenzenesulfonic acid.

Among these, preferred aromatic compounds include benzenesulfonic acid, sodium benzenesulfonate, p-toluenesulfonic acid, I)-}sodium toluenesulfonate, p-toluenesulfinic acid, sodium p-toluenesulfinate, benzenesulfinic acid, 5 - Sodium sulfoisophthalate,
2-Sulfobenzoic acid, 4-amino-m-}luenesulfonic acid, 4-amino-m-toluenesulfonic acid sodium, 1
Examples include naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, sodium 5-amino-l-naphculenesulfonic acid, and p-chlorobenzenesulfonic acid.

The photosensitive diazo cocondensation resin according to the present invention can be prepared by a known method,
For example, Photographic Science and Engineering (Photo. Scl. Eng.)
Volume 17, page 53 (1973), U.S. Patent No. 2,06
3,631 and No. 2,679,498, in sulfuric acid, phosphoric acid, or hydrochloric acid, the diazonium salt represented by the general formula (I [[), the general formula [ (2)] and aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones such as acetone and acetophenone.

Further, the charging molar ratio of the aromatic diazo compound represented by the general formula (II[) to the aromatic compound represented by the general formula [■] is 1:0.1 to 0.1:1, preferably 0.5
:1 to 1:0.2, more preferably 1:1 to 1:0.2
It is. In this case, the molar ratio of the sum of the aromatic diazo compound represented by the general formula (III) and the aromatic compound represented by the -i formula (IV) to aldehydes or ketones is usually 0. 6-1.5:L preferably 0.7
A diazo cocondensation resin can be obtained by charging at a temperature of 1.4:t and reacting at a low temperature for a short time, for example, about 3 hours.

The counter anion of the diazo resin used in the present invention is
Hexafluorophosphoric acid and tetrafluoroboric acid.

Specific examples of the diazo cocondensation resin in the present invention include benzenesulfonic acid-4-diazo 4'methoxydiphenylamine hexafluorophosphate monoformaldehyde resin,
Sodium benzenesulfonic acid-4-diazo 4'-methoxydiphenyl phosphoric acid hexafluoride-formaldehyde resin, p-1 luenesulfonic acid-4-diazo 4'
-Methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, sodium benzenesulfonic acid 4-diazo 3-methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, m-benzenedisulfonic acid disodic acid-4- Diazo 4'-methoxydiphenylamine/hexafluorinated phosphate monoformaldehyde resin, 4-diazo 4'-methoxydiphenylamine/hexafluorinated phosphate monoformaldehyde resin, 1- Naphthalenesulfonic acid-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, -Amino-2-naphthalenesulfonic acid-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate - Formaldehyde resin, 5-Agonol-Naphthalenesulfonic acid sodium - 4-Diazodiphenylamine hexafluorophosphate - Formaldehyde resin, 4-Amino-M-}luenesulfonic acid soda -
4-diazo 4'-methoxydiphenylamine/tetrafluoroborate-formaldehyde resin, 2-sulfobenzoic acid-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, p-toluenesulfone Acid soda-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, sodium benzenesulfonate-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, p
-}Luenesulfinic acid-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate monoformaldehyde resin, p-}Sodium luenesulfinate-4-diazo 4'-methoxydiphenylamine/hexafluoride phosphate-formaldehyde resin, sodium benzenesulfinate-4-diazo 4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, etc. Of these, preferred are benzenesulfonic acid-4-diazo 4 ′
-Methoxydiphenyla fruit/hexafluorophosphate -Formaldehyde resin, sodium benzenesulfonate -4-diazo 4'-methoxydiphenyla fruit/hexafluorophosphate monoformaldehyde resin, p-chlorobenzenesulfone Acid = 4-diazo 4'-methoxydiphenylamine hexafluorophosphate-formaldehyde resin, 1-naphthalenesulfonic acid-4-diazo 4'-methoxydiphenylamine hexafluorophosphate monoformaldehyde Resin, 4-Ano-m-toluenesulfonic acid soda-4-diazo 4'-methoxydiphenylamine/tetrafluoroborate monoformaldehyde resin, p-1 toluenesulfonic acid-4-diazo-4'-methoxydiphenylamine・Hexafluorophosphate monoformaldehyde resin, p-1 luenesulfonic acid soda-4-diazo 4'-methoxydiphenylamine ・Hexafluorophosphate-formaldehyde resin,
p-toluenesulfinic acid-4-diazo 4'-methoxydiphenylamine hexafluorophosphate formaldehyde resin.

The diazo cocondensation resin of the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions, but in order to effectively serve the purpose of the present invention, has a molecular weight of about 400 to 10,000
can be used, but preferably about 800 to 5
．． 0 0 0 is suitable.

The photosensitive diazo resin used in the present invention is usually contained in the photosensitive layer in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

The photosensitive diazo cocondensation resin described above is preferably used in combination with an alkali-soluble or expandable lipophilic polymer compound as a binder resin.

Examples of this lipophilic polymer compound include copolymers having a molecular weight of usually 20,000 to 200,000 and having the monomers shown in items 11 to a below as structural units.

+1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes having an aromatic hydroxyl group, such as N-
(4-Hydroxyphenyl>acrylamide or N-(
4-hydroxyphenyl) methacrylamide, 0-, m
-, p-hydroxyphenylacrylate or methacrylate, 0-, m-, p-hydroxystyrene, (2
) Acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, etc. Acid, (4) Methyl acrylate, ethyl acrylate, probyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-
(Substituted) alkyl acrylates such as dimethylaminoethyl acrylate, (5) Methyl methacrylate, ethyl methacrylate, proyl methacrylate, butyl methacrylate,
(6) acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, monoethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, provil Vinyl ethers such as vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (9) Styrene, α-methylstyrene, and methylstyrene. , styrenes such as chloromethylstyrene, αω vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, probyl vinyl ketone, phenyl vinyl ketone, αυ olefins such as ethylene, propylene, isobutylene, putadiene, isobrene, etc. N-vinylpyrrolidone, N-vinylrubazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., αη maleimide, N-acryloyl acrylamide,
Unsaturated imides such as N-acetylmethacrylamide, N-propionylmethacrylamide, N-(p-chlorobenzoyl)methacrylamide, 04) m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide, unsaturated sulfonamides such as N-(p-}luenesulfonyl)methacrylamide;

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, a copolymer having a hydroxyl group containing the monomers listed in (l) and (2) above is preferable,
More preferred are copolymers having aromatic hydroxyl groups.

The copolymer preferably contains an unsaturated carboxylic acid listed in (3), and the preferred carboxylic acid value of the copolymer is 0 to 3 meq/g, more preferably 0.
5 ~1. It is 5meq/g.

The preferred molecular weight of the above copolymer is 10,000 to 150,000.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolafuku resin, natural resin, etc. may be added to the above copolymer as necessary.

The lipophilic polymer compound used in the present invention is usually 40 to 99% by weight, preferably 50 to 99% by weight in the solid content of the photosensitive composite bottom.
Contains 95% by weight.

Next, a synthesis example of the above lipophilic polymer compound will be shown.

(Combination of lipophilic polymer compound 1) N-(4-hydroxyphenyl) methacrylamide 18
g1 Acrylonitrile 13g1 Ethyl acrylate 66
g, 8.6 g of methacrylic acid and 1.642 g of abbisisobutyronitrile were dissolved in 112 ml of a 1:1 mixed solution of acetone and methanol, and the mixture was purged with nitrogen and then heated at 60° C. for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 88 g of lipophilic polymer compound 1.

When the molecular weight of this lipophilic polymer compound 1 was measured by gel permeation chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was 75,000.

(Synthesis of lipophilic polymer compound 2) 5.0 g of 2-hydroxyethyl methacrylate, N-(
20 g of 4-hydroxyphenyl)acrylamide, 60 g of methyl methacrylate, 8.0 g of methacrylic acid, and 1.
A mixture of 2 g of benzoyl peroxide was added to 300 g of ethylene glycol monomethyl ether heated to 100°C.
It dripped over time.

After completion of dropping, add 30% ethylene glycol monomethyl ether
0 g and 0.3 g of benzoyl peroxide were added thereto, and the reaction was continued for 4 hours. After the reaction is complete, dilute with methanol and add 51 ml of water.
The resulting white precipitate was collected by filtration and dried to obtain 86 g of lipophilic polymer compound 2.

When the molecular weight of this lipophilic polymer compound 2 was measured by CPC, the weight average molecular weight was 82,000.

(Synthesis of lipophilic polymer compound 3) N-(4-hydroxyphenyl)methacrylate 20
20 g of g,2-cyanoethyl methacrylate > 50 g of ethyl methacrylate, a mixture of 10 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise to ethylene glycol monomethyl ether in the same manner as in the case of lipophilic polymer compound 2 to obtain lipophilic properties. 85g of polymer compound 3 was obtained.

When the molecular weight of this lipophilic polymer compound 3 was measured by GPC, the weight average molecular weight was 69,000.

The photosensitive composition used in the present invention may further include a dye. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, one that changes color tone by reacting with free radicals or acids can be preferably used.

Here, "the color tone changes" includes both a change from colorless to a colored tone, and a change from a color to colorless or a different colored tone. Preferred dyes are those that change color when exposed to acids and salts.

For example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Bioleft, Brilliant Green, Ethyl Violet, Methyl Violet, methyl green,
Triphenyl typified by erythrosin B, peishoxfuchsin, malachite green, oil red, m-cresol barfur, rhodamine B, auramine, (4-p-diethylaminophenyl)iminaphthoquinone, cyanop-diethylaminophenyl acetanilide, etc. Methane-based, diphenylmethane-based, oxidine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes are cited as examples of color-changing agents that change from colored to colorless or different colored tones.

On the other hand, examples of color changing agents that change from colorless to colored include leuco dyes, triphenyla straw, diphenylamine, 0-chloroaniline, 1,2,3-triphenylguanicine, naphthyla straw, diaminodiphenylmethane, p , p'-bis~dimethylaminodiphenylamine,
1.2-dianilinoethylene, p,p',p'-1-lys-dimethylaminotriphenylmethane, p. p'-bis-dimethylaminodiphenylmethylion, p, pp
#mono-triamino-0-methyltriphenylmethane, p,
p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p. p'. Examples include primary or secondary arylamine dyes represented by p'-triaξnotriphenylmethane.

Particularly preferably triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, especially Victoria Pure Blue BOH.

The above-mentioned dye is usually contained in the photosensitive composition at about 0.0%. 5 to about IO
It is preferable to contain the amount by weight, more preferably about 1% by weight.
Contain up to 5% by weight.

Various additives can be further added to the photosensitive composition used in the present invention.

For example, alkyl ether J (
(e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L-64 (Asahi Denka Co., Ltd.)), plasticizers to impart flexibility and abrasion resistance to the coating film. (e.g. butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or meccrylic acid) (oricomers and polymers of
Alcohol-based half esters of styrene-maleic anhydride copolymers described in Japanese Patent Publication No. 1983-3-2
6 2 6 4 2), stabilizers [e.g. phosphoric acid, phosphorous acid, organic acids (
citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.).

The amount of these additives added varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

Such a photosensitive composition is coated on a support. Examples of the support include aluminum plates or alloy plates thereof, metal plates such as zinc plates, steel plates, and stainless steel plates, and plastics such as polyethylene terephthalate and polypropylene.

When the photosensitive composition of the present invention is applied to the production of photosensitive lithographic printing plates, it is used by being provided on a support such as an aluminum or alloy plate thereof.

The support used in the photosensitive lithographic printing plate is as follows:
Paper, plastics (e.g. polyethylene, polypropylene, polystyrene, etc.), laminated paper, plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose probionate, Plastic films, such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl acetal, etc.
Examples include paper or plastic films laminated or vapor-deposited with the metals mentioned above, steel plates plated with aluminum or chrome, and among these, aluminum and aluminum-coated composite supports are particularly preferred.

Further, the surface of the aluminum material is preferably roughened for the purpose of increasing water retention and improving adhesion with the photosensitive layer.

Examples of the surface roughening method include generally known methods such as brush polishing, ball polishing, electrolytic etching, chemical etching, liquid honing, and sandblasting, and combinations thereof. Preferably, brush polishing, electrolytic etching, and chemical Target etching and liquid honing are mentioned, among which roughening methods that involve the use of electrolytic etching are particularly preferred. In addition, the electrolytic bath used in electrolytic etching is an aqueous solution containing an acid, an alkali, or a salt thereof, or an aqueous solution containing an organic solvent. Liquid is preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary. It is desirable that the aluminum plate thus obtained is subjected to anodizing treatment, and particularly preferred is a method of treatment in a bath containing sulfuric acid or phosphoric acid. Further, if necessary, surface treatment such as pore sealing treatment with an alkali silicate or hot water, or immersion in a water-soluble polymer compound or potassium fluorozirconate aqueous solution can be performed.

In order to provide the above-mentioned photosensitive composition on a support, predetermined amounts of the photosensitive diazo cocondensation resin, lipophilic polymer compound, and optionally various additives are mixed in a suitable solvent (methyl cellosolve, ethyl cellosolve, etc.). Dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ■-methoxy-2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl acetamide, cyclohexanone, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide, water or a mixture thereof, etc.) to prepare a coating solution of the photosensitive composition,
This may be applied onto a support and dried. The solid content concentration of the photosensitive composition during coating is preferably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition may be approximately 0.2 to 10 g/m (dry weight).

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original with a halftone image or the like and subsequent development with an aqueous alkaline developer substantially free of organic solvents provides a negative relief image on the original.

In the present invention, the alkaline agent for the aqueous alkaline developer that does not substantially contain an organic solvent includes sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Inorganic alkaline agents such as ammonium triphosphate, diammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium borate, ammonium borate, ammonia, etc., and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, etc. triethylamine, monoisopropylamine, diisoprobylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. There are organic amine compounds such as these, which can be used alone or in combination.

Among these, sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine, triethanolamine, etc. are preferred, and sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, etc. are particularly preferred. These may be used alone or in combination with other alkaline agents.

The content of these alkaline agents in the developer composition is 0.0
5-10% by weight, preferably 0. 1 to 7% by weight is suitable.

Further, an anionic surfactant may be added to the developer composition as necessary. Furthermore, an organic solvent can also be added. Examples of anionic surfactants include higher alcohol sulfate esters having 8 to 22 carbon atoms such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of uralyl alcohol sulfate, and sulfonic sodium alkyl sulfate. Salts, such as the sodium salt of cetyl alcohol phosphate ester, etc., such as the sodium salt of dodecylbenzenesulfonic acid, the sodium salt of isopropylnaphthalenesulfonic acid, the sodium salt of metanitobenzenesulfonic acid, etc. Alkylaryl sulfonates, such as C+J3aCON(CHz)CHzCHzSOJa
Sulfonic acid salts of alkylamides such as, for example, sulfonic acid salts of dibasic fatty acid esters such as sodium sulfosuccinic acid dioctyl ester and sodium sulfosuccinic acid dihexyl ester.

It is appropriate that the anionic surfactant be contained in an amount of 0.1 to 5% by weight based on the total weight of the developer at the time of use. If it is less than 0.1% by weight, the effectiveness of its use will be lowered, and if it is more than 5% by weight, for example, the dye contained in the photocurable photosensitive liquid may elute excessively (color loss). This results in disadvantages such as deterioration of mechanical and chemical strength such as abrasion resistance of photocured images.

In the present invention, the aqueous alkaline developer can also contain a very small amount of organic solvent.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, preferably 5% by weight or less. For example, l-phenylethanol, 2-
phenylethanol, 3-phenylbrovanol-1,
4-phenylbutanol-1, 4-phenylbutanol-2, 2-phenylbutanol-1, 2-phenoxyethanol, 2-penzyloxyethanol, 0-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p- Examples include methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol.

The content of organic solvent is 2% based on the weight of the developer at the time of use.
It is not more than 1% by weight, preferably not more than 1% by weight.

Furthermore, additives such as an antifoaming agent and a water softener can be added as required. Examples of water softeners include Na2P20v+ NasPzO:++Na3
P30q, Na. Polyphosphates such as OaP (NaO3P) POJa2, Calgon (sodium polymetaphosphate),
For example, ethylenediaminetetraacetic acid, its potassium salt,
Its sodium salt; diethylenetriaminepentaacetic acid,
Its potassium salt, sodium salt; triethylenetetraξ
Nitrilotriacetic acid, its potassium salt, its sodium salt; Hydroxyethylethylene diξethanetriacetic acid, its potassium salt, its sodium salt; Nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diagonocyclohexanetetraacetic acid, its Potassium salts, sodium salts thereof; Aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid, potassium salts thereof, sodium salts thereof, etc. can be mentioned.

The optimal amount of such water softeners varies depending on the hardness of the hard water used and the amount used, but the general amount used is 0.01 to 5% by weight in the developer when used. , more preferably in a range of 0.01 to 0.5% by weight.

Further, in the present invention, the aqueous alkaline developer may contain a reducing inorganic salt if necessary. The above-mentioned reducing inorganic salt has a reducing action, preferably a water-soluble inorganic salt, and particularly preferably a salt of a lower oxygen acid. For example, sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, lithium sulfite, magnesium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite,
Sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite,
Examples include phosphites such as potassium dihydrogen phosphite. These may be used alone or in combination. Among these, preferred are alkali metal salts of sulfite. The content of these reducing inorganic salts in the developer composition is 0.001
-30% by weight, preferably 0.01 - IO% by weight.

Further, in the present invention, the aqueous alkaline developer may contain a water-soluble pyrazolone compound, an alkali-soluble mercabuto compound, a 1,3-dihydroxy aromatic compound, or a salt thereof, if necessary. These may be used alone or in combination. The content in the developer composition is preferably 10% by weight or less. The higher the content, the higher the ability to prevent stains in non-image areas, but the higher the content, the higher the ability to prevent stains in non-image areas. However, if the content is more than 10%, the photocured areas of the photosensitive layer will be damaged. Mechanical strength deteriorates, and when applied to lithographic printing plates, it leads to a decrease in stiffness resistance.

Examples of the above alkali-soluble mercapto compounds include mercaptoacetic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid.
Mercaptoprobionic acid, 4-mercaptobutanoic acid, 2
, 4-dimercaptobutanoic acid, 2-mercaptotetradecanoic acid, 2-mercapto ξ listic acid, mercaptosuccinic acid, 2.3-dimercaptosuccinic acid, cysteine, N
-7 cetylcysteine, N- (2-mercaptopropionyl)glycine, N-(2-mercapto-2-methylpropionyl)glycine, N- (3-mercaptopropionyl)glycine, N-(2-mercapto-2- Methylprobionyl) cysteine, penicillane, N-acetylbenicillane, glycine-cysteine-glutamine condensate, N-(2,3-dimercaptopropionyl)
Glycine, 2-mercaptonicotinic acid, thiosalicylic acid,
3-mercaptobenzoic acid, 4-mercaptobenzoic acid, 3
-carboxy 2-mercaptopyridine, 2-mercaptobenzothiazole-5-carboxylic acid, 2-mercapto-3-phenylpropenoic acid, 2-mercapto-5-carboxyethyl imidazole, 5-mercapto-1-(4
-carpoxyphenyl)tetrazole, N- (3,5
-dicarboxyphenyl>-2-mercabutotetrazole, 2- (1,2-dicarboxyethylthio)-5-
Mercapto-1.3.4-thiadiazole, 2-(5-
Mercapto-1.3.4-thiadiazolylthio)hexanoic acid, 2-mercaptoethanesulfonic acid, 2,3-dimercapto-1-propanesulfonic acid, 2-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid , 3-mercabuto-4(2-sulfophenyl)-1.2
．． 4-triazole, 2-mercaptobenzothiazole-5-sulfonic acid, 2-mercaptobenzimidazole=6-sulfonic acid, mercaptosuccinimide, 4-mercaptobenzenesulfonamide, 2-mercaptobenzimidazole-5-sulfonamide, 3 -Mercapto-
4- (2- (methylanosulfonyl)ethoxy)
Toluene, 3-mercapto-4-(2-(methylsulfonylamino)ethoxy)toluene, 4-mercapto N-(p-methylphenylsulfonyl)penzamide, 4-mercaptophenol, 3-mercaptophenol, 2-mercaptophenol, 3,,4-dimercaptotoluene, 2-mercaptohydroquinone, 2-thiouracil, 3-hydroxy-2-mercaptoviridine,
4-hydroxythiophenol, 4-hydroxy-2-
Mercaptoviridine, 4,6-dihydroxy-2-mercaptopyrigodine, 2,3-dihydroxybubutylmercabutane, 2-mercapto-4-octylphenol methanesulfonylaminoethyl ether, 2-mercapto-4-octylphenol or its alkali metal salts,
Examples include alkaline earth metal salts and organic amine salts.

Particularly preferred are thiosalicylic acid, N-(2
, 3-dimercaptoprobionyl> glycine, 2- (
1.2-dicarboxyethylthio)-5-mercapto-
1.3.4-thiadiazole, N-(2-mercapto-
2-methylprobionyl) cysteine, cysteine, and the like.

On the other hand, examples of the above-mentioned 1,3-dihydroxy aromatic compounds include resorcin, 1,3-dihydroxynaphthalene, 2-methylresorcin, 1,3-dihydroxy-2-
Examples include methylnaphthalene, 2-probylresorcinol, 2-ethylresorcinol, L3-dihydroxy-2,7-dimethylnaphthalene, or alkali metal salts, alkaline earth metal salts, and organic amdan salts thereof.

The pH of the aqueous alkaline developer used in the present invention is 11 or higher, preferably 12 or higher.

Such an aqueous alkaline developer that does not substantially contain an organic solvent is described in, for example, JP-A No. 59-84241 and JP-A-57-192952, etc., in which a positive planographic printing plate is imagewise exposed. After that, the developer composition used for development can be used.

If necessary, after development, washing with water, desensitizing it, or directly desensitizing it, or treating it with an aqueous solution containing an acid, or desensitizing it after processing with an aqueous solution containing an acid. Also good. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount and the alkaline concentration decreases, or the alkaline concentration is decreased by air due to long-term operation of the automatic developer. Processing capacity will decrease, but in that case,
2004, a replenisher may be used to restore throughput.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

〔Effect of the invention〕

Since the image forming method of the present invention uses an aqueous alkaline developer that does not substantially contain organic solvents during development, there are health problems such as toxicity and odor during work, and safety problems such as fire and gas explosion. Furthermore, there are no problems such as pollution caused by waste liquid, and it can be implemented at low cost.

Furthermore, when the image forming method of the present invention is applied to a lithographic printing plate, the negative-working lithographic printing plate can be developed using an aqueous alkaline developer known as a developer for positive-working lithographic printing plates. For this reason, when processing both positive-tone planographic printing plates and negative-tone planographic printing plates, it is necessary to prepare developer compositions to suit each, change the developer compositions, or use two types of developer in advance. It is possible to eliminate the hassle of preparing assembly materials and development processing equipment, and improve work efficiency.
Equipment costs, installation space, etc. are significantly improved.

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples.

[Combined precepts]

Synthesis Example 1 Synthesis of co-condensed diazo resin 1 Sodium benzenesulfonate 4.5 g (0.02
5 mol) and 24.3 g (0.075 mol) of 4-diazo 4'-methoxydiphenyla noble sulfate were dissolved in 90 g of concentrated sulfuric acid under water cooling. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) was slowly added. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was poured into 11 ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was
00 in pure water, and add 10.0 in this solution. A cold concentrated aqueous solution of 5 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and dissolved in 300% pure water. Add this liquid to 1 3. A cold concentrated aqueous solution of 7 g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water, and then dried at 30° C. for 1 day and night to obtain a co-condensed diazo resin 1.

The molecular weight of this co-condensed diazo resin 1 was measured by GPC (gel permeation chromatography), and the weight average molecular weight was about 2,300.

Synthesis Example 2 Synthesis of co-condensed diazo resin 2 Sodium benzenesulfonate of co-condensed diazo resin 1 was converted into p-
}Luensulfinic acid 3.9 g (0.0 2 5
Co-condensed diazo resin 2 was obtained in the same manner as in the case of the synthesis of co-condensed diazo resin 1 except that the amount was changed to (mol).

When the molecular weight was measured by GPC, the weight average molecular weight was about 2,500.

Synthesis Example 3 Synthesis of co-condensed diazo resin 3 4-diazo 4'-methoxydiphenylamine sulfate of co-condensed diazo resin 1 was added to 4-diazodiphenylamine sulfate 2 2.0 g (0.0 7 Co-condensed diazo resin 3 was obtained in the same manner as in the case of combining co-condensed diazo resin 1, except that the amount was changed to 5 mol). When the molecular weight was measured by GPC, the weight average molecular weight was about 2450.

Synthesis Example 4 Synthesis of Co-Condensed Diazo Resin 4 or Sodium Benzene Sulfonate of Co-Condensed Diazo Resin 1
Sodium amino-m-1-luenesulfonate 5.2 g
(0.0 2 5 mol) and ammonium hexafluorophosphate was replaced with ammonium tetrafluoroborate 8.
Co-condensed diazo resin 4 was obtained in the same manner as in the case of co-condensed diazo resin 1 except that the amount was changed to 81 g. When measured by GPC, the weight average molecular weight was approximately 2100.

Synthesis Example 5 Synthesis of co-condensed diazo resin 5 or sodium benzenesulfonate of co-condensed diazo resin 1,
-Naphthalenesulfonic acid6. Co-condensed diazo resin 5 was obtained in the same manner as in the synthesis of co-condensed diazo resin 1, except that the amount was changed to 1 g (0.025 mol).

The weight average molecular weight was about 2000 as determined by GPC.

Synthesis Example 6 Comparison of Diazo Resin 6 (Comparative Diazo Resin) 29 g (0.1 mol) of p-diazodiphenylamine ξane sulfate was dissolved in 90 g of concentrated sulfuric acid under water cooling. Add 2.7g (0.0
9 mol) of paraformaldehyde was slowly added dropwise.

At this time, the reaction temperature was made not to exceed 10°C. After that, stirring was continued for 2 hours under water cooling.

500 ml of ethanol was added dropwise to the reaction mixture under water cooling, and the resulting precipitate was filtered off. After washing with ethanol, this precipitate was dissolved in 100% pure water, and 6.8% was added to this solution.
A cold concentrated aqueous solution of 1 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and filtered to 150 m
1 of pure water.

To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at a temperature of 30° C. for one day and night to obtain diazo resin 6.

When the molecular weight of this diazo resin 6 was measured by GPC, it was found to be about 2,200 in terms of weight average molecular weight.

Combination example 7 Combination of diazo resin 7 (comparative diazo resin) 22 g (0.075 mol) of p-diazodiphenylamine sulfate and 2 g (0.025 mol) of phenol were added to 90 g of concentrated sulfuric acid under water cooling. 2.7 g (0.09 mol) dissolved in this (D?&)
of paraformaldehyde was slowly added dropwise. At this time, the reaction temperature was made not to exceed 10°C. After that, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered off. After washing with ethanol, this precipitate was dissolved in 100-pure water, and 6.8 g
A cold concentrated aqueous solution of zinc chloride was added. The formed precipitate was filtered, washed with ethanol, and dissolved in 150-pure water.

To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at a temperature of 30° C. for one day and night to obtain diazo resin 7.

When the molecular weight of this diazo resin 7 was measured by GPC, it was found to be 2200 in terms of weight average molecular weight.

〔Example〕

Examples 1 to 6, Comparative Examples 1 to 3 An aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically ethoched in a 2% hydrochloric acid bath at 25°C and at a current density of 3 A/dm2, and after washing with water, 3 in a 15% sulfuric acid bath
Anodic oxidation treatment was performed for 2 minutes at 0°C and 1.5A/dm2. Next, at 85°C in a 1% sodium metasilicate aqueous solution,
The pores were sealed for 30 seconds, washed with water, and dried to obtain an aluminum plate for planographic printing. A photosensitive solution with the following composition was applied to this aluminum plate and the film weight after drying was 1.5 g/n? It was applied and dried at 80°C for 3 minutes.

Photosensitive liquid Lipophilic polymer compound 1-2 5.0g Diazo resin 1-7 0.6g Victoria Viewer Blue BOH O. 1 g (manufactured by Hodogaya Chemical ■) Jurimer AC-10L 0.3 g (manufactured by Nippon Pure Chemical Industries, Ltd.) Methyl cellosolve 100 Note that combinations of lipophilic polymer compounds and diazo resins are shown in Table 1.

The obtained photosensitive lithographic printing plate was subjected to 10 tests using an ultra-high pressure mercury lamp for 3 questions.
After exposure for 30 seconds from a distance of 0.0 mm, development was performed at 25° C. for 45 seconds using the following developer to obtain a lithographic printing plate.

Composition of developer These plates were examined for diazo residue. Diazo residue was visually determined by exposing half of the non-image area of the printing plate thus obtained and comparing it with the area that was not exposed again.

In addition, forced storage (55℃, humidity 15%RH or less for 3 days)
After that, the plate was made in the same manner as above, and KO manufactured by Heidelberg was used.
Printing was performed on high-quality paper using a commercially available ink using an R-type printing machine, and print stains in non-image areas were examined. These results are summarized in Table 1.

As can be seen from Table 1, by using the image forming method of the present invention, good printed matter without printing stains can be obtained using an aqueous alkaline developer that does not substantially contain an organic solvent.

table 1 A : Not at all C ：Slightly more B :rare D :many

Claims (1)

[Claims] The following general formulas [I] and [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (Formula In the middle, R^1, R^2 and R^3 are each a hydrogen atom,
Alkyl group or alkoxy group, R^4 and R^5 are each hydrogen atom, alkyl group or phenyl group, X is PF_6
or BF_4, Y is -NH-, -S- or -O-, Z has at least one group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group as a substituent. After imagewise exposure of a photosensitive layer containing a co-condensed diazo resin having a structural unit represented by a phenylene group or a naphthylene group with or without other substituents, the photosensitive layer contains substantially no organic solvent. An image forming method characterized by developing with an aqueous alkaline developer.