JPH09325502A - Developing method of photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep a balance between a performance of an obtained cured body and a developing characteristic in a specific water developable photosensitive resin composition by using water and a nonionic surfactant as a developer for a specified water developing photosensitive resin composition. SOLUTION: A hydrophilic crosslinking particle copolymer, a thermoplastic block copolymer, a photopolymerizable unsatd. monomer and a photopolymerization initiator are incorporated in the water developing photosensitive resin composition, and the water and the nonionic surfactant are incorporated in an aq. developer. The hydrophilic crosslinking particle copolymer is composed of 10-95mol.% aliphat. conjugated diene monomer and 0.1-30mol.% monomer, etc., containing a functional group such as carboxyl group and obtained by polymerizing 100mol.% monomer mixture totally. The thermoplastic block copolymer is composed of 1-40mol.% thermoplastic nonelastomeric block X having >=20 deg.C glass transition temp. and 60-99mol.% elastomer Y having <=10 deg.C glass transition temp.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for developing a specific water-developable photosensitive resin composition.

[0002]

2. Description of the Related Art In the present specification, "printing plate" means a plate material having a relief after being exposed and developed, and it is a "resin plate".
Means a so-called green plate before exposure and development.

[0003] The photosensitive resin plate in the method of manufacturing a printing plate for flexographic printing is preferably provided for ease of handling, worker's health,
From the viewpoint of safety and environmental pollution, it is preferable that after exposure to ultraviolet rays, development can be performed with water rather than an organic solvent in order to obtain a desired relief. On the other hand, ink used for flexographic printing with a relief printing plate obtained from a photosensitive resin plate is generally an aqueous ink or an alcoholic ink. Therefore, the relief obtained after exposure and development is required to have chemical resistance to the solvent of the ink. Furthermore, it is desired that the characteristics of these printing plates do not change before and after printing.

To satisfy these characteristics, the present inventors have already (i) a three-dimensional crosslinked polymer, (ii) a copolymer having a conjugated diene unit in the composition, (iii) a basic nitrogen-containing compound. , (Iv) a photosensitive resin composition containing a photopolymerizable monomer and (v) a photopolymerization initiator as a base,
Obtained a patent (Japanese Patent Publication No. 5-6178). This photosensitive resin composition exhibits excellent properties and is highly evaluated in the printing industry.

The photosensitive resin composition of the above patent is exposed through a negative film 3 after forming a layer as a photosensitive resin layer 2 on a substrate 1 as shown in FIG. After exposure, a relief image is formed by developing with water, which is a feature of the above patent.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have improved the rubber elasticity and printing durability of a photosensitive resin composition described in JP-B-5-6178 and a photosensitive resin flexographic plate using the same. Although intensive studies have been carried out in order to achieve it, there has been a problem that the reproducibility and image quality of a water-developable image are deteriorated when trying to obtain plate performance of a flexographic plate suitable for the purpose. The present invention resides in improving these problems.

[0007]

Means for Solving the Problems The inventors of the present invention have investigated a developing solution, and by adding a nonionic surfactant mainly to water, the above-mentioned drawbacks, that is, image reproducibility and image quality. Further, they have found that a developing method can be obtained in which the water developability is improved and at the same time, the elasticity, printing resistance, mechanical strength, etc. of a flexographic plate are maintained, and the present invention has been completed. That is, the present invention provides a method for developing a water-developable photosensitive resin composition, which comprises exposing the water-developable photosensitive resin composition in an image mode and then developing and removing the unexposed portion with an aqueous developer. A resin composition containing (A) 10 to 95 mol% of an aliphatic conjugated diene monomer, one or more kinds of functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group and a phosphoric acid group .1-30
Mol%, 0.1 to 20 mol% of monomers having two or more addition-polymerizable groups, excluding aliphatic conjugated diene monomers, and 0 to 70 mol% of other copolymerizable monomers. However, a hydrophilic crosslinked particle copolymer obtained by polymerizing a monomer mixture in which +++ = 100 mol%, (B) a thermoplastic non-elastomeric block X having a glass transition point of 20 ° C. or higher is 1 to 40 mol%. And a thermoplastic block copolymer containing 60 to 99 mol% of an elastomer Y having a glass transition point of 10 ° C. or lower and having an XY-X type structure or an XY type structure, (C) photopolymerizable A method for developing a water-developable photosensitive resin composition, which contains an unsaturated monomer and (D) a photopolymerization initiator, and the aqueous developer contains water and a nonionic surfactant. Exist in.

The monomer constituting the hydrophilic cross-linked particle copolymer (A) is an aliphatic conjugated diene monomer, for example, 1,3-
Examples thereof include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, chloroprene and the like. The aliphatic conjugated diene monomer preferably has 4 to 6 carbon atoms, more preferably 4 to 6 carbon atoms.
5 "Conjugated diene monomer" means -C = C-C =
It is a monomer having a C-bond and having two double bonds, but under normal polymerization conditions it is a monomer which acts so as to have one double bond. The monomer having two or more addition-polymerizable groups described below is different from the monomer because all the addition-polymerizable groups contribute to the polymerization reaction during the polymerization.

The content of the monomer in the crosslinked particle copolymer (A) is 10 to 95 mol%, preferably 30 to 90 mol%. When the content of the component is less than 10 mol%, the strength of the composition polymer after photocuring is low. Also, 95 mol%
When it is more, the water developability of the photosensitive resin composition is poor.

The monomer constituting the copolymer (A) is a monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group and a phosphoric acid group.

As the carboxyl group-containing monomer, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid; (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid, Unsaturated polycarboxylic acids (anhydrides) such as mesaconic acid; Free carboxyl group-containing esters of the unsaturated polycarboxylic acids; Free carboxyl group-containing nitriles of the unsaturated polycarboxylic acids; Examples include free carboxyl group-containing amides.

Further, the monomer represented by the following general formula (I):

[0013]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group, R 1
² represents an alkylene group having 3 to 20 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms (eg, propylene group, butylene group, etc., 1 represents an integer of 1 to 20, preferably 1 to 10) Good.

Specific examples of the compound represented by the general formula (I) include the following compounds: CH ₂ ═C
_{HCOO-C 3 H 6 COOH,} CH 2 = CHCOO-C 4 H
₈ COOH, CH ₂ = CHCOO-C ₅ H ₁₀ COOH, C
_{H 2 = CHCOO- (C 3 H} 6 COO) 2 -H, CH 2 = CH
_{COO- (C 4 H 8 COO)} 2 -H, CH 2 = CHCOO-
_{(C 5 H 10 COO) 2} -H, CH 2 = CHCOO- (C 5 H 10
_{COO) 3 -H, CH 2 =} CHCOO- (C 5 H 10 COO) 4
_{-H, CH 2 = CHCOO- (C} 5 H 10 COO) 5 -H, C
_{H 2 = C (CH 3)} COO-C 3 H 6 COOH, CH 2 = C (C
_{H 3) COO-C 4 H} 8 COOH, CH 2 = C (CH 3) COO
_{-C 5 H 10 COOH, CH 2} = C (CH 3) COO- (C 3 H 6
_{COO) 2 -H, CH 2 =} C (CH 3) COO- (C 4 H 8 CO
_{O) 2 -H, CH 2 =} C (CH 3) COO- (C 5 H 10 COO) 2
_{-H, CH 2 = C (CH} 3) COO- (C 5 H 10 COO) 3 -
_{H, CH 2 = C (CH} 3) COO- (C 5 H 10 COO) 4 -H,
_{CH 2 = C (CH 3)} COO- (C 5 H 10 COO) 5 -H.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth). Acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono
(Meth) acrylate, polyalkylene glycol mono
Mono (meth) acrylates of polyhydric alcohols such as (meth) acrylate (the number of polyalkylene glycol units is, for example, 2 to 12); N-hydroxymethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide,
N-2-hydroxypropyl (meth) acrylamide, N
Unsaturated hydroxyl group-containing amides such as -3-hydroxypropyl (meth) acrylamide; unsaturated alcohols such as (meth) allyl alcohol.

Of these hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and the like are preferable.

Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid group and 2-acrylamido-2-methylpropane sulfonic acid.

As the phosphate group-containing monomer, mono (2-
(Meth) acryloyloxyethyl) acid phosphate and the like can be mentioned.

The above monomers may be used alone or in combination of two or more, depending on the purpose. The content of the monomer component in the crosslinked particle copolymer is 0.1 to 30 mol%, preferably 0.5 to 20 mol%. If the content of the components is less than 0.1 mol%, the resulting photosensitive resin composition will have poor water developability, and if it is more than 30 mol%, the resulting composition will be hard and brittle, both of which are not preferred.

The monomer constituting the copolymer (A) is a monomer having two or more addition-polymerizable groups other than the above aliphatic conjugated diene monomer. The presence of this monomer causes three-dimensional crosslinking in the copolymer. Specific examples of such, esters of polyols with (meth) acrylic acid, such as ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol di Methacrylate, propylene glycol diacrylate, divinylbenzene, trivinylbenzene, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, 1,4
Examples include butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. These polyfunctional polymerizable monomers can be used alone or in combination of two or more.

The content of the monomer component is 0.1 to 20 mol%
And preferably 0.5 to 10 mol%. When the content of the components is less than 0.1 mol%, the water developability of the composition is poor. Also, 2
When it is more than 0 mol%, the compatibility between the particulate polymer and the photopolymerizable monomer is poor and the processability is deteriorated. Further, the strength of the composition polymer after photocuring is significantly reduced.

The monomer component constituting the copolymer (A) is
The compound is not particularly limited as long as it is a compound other than the above monomers and having one addition-polymerizable group. Specific examples include styrene; α-methylstyrene; vinyltoluene; acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, n.
-Propyl (meth) acrylate, 2-ethylhexyl
(Meth) acrylate; (meth) acrylic acid, crotonic acid,
Unsaturated (mono) carboxylic acids such as cinnamic acid; (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid,
Unsaturated polycarboxylic acids (anhydrides) such as mesaconic acid; monomethyl ester, monoethyl ester, monopropyl ester, monohexyl ester, monooctyl ester, dimethyl ester, diethyl ester, dipropyl ester of the aforementioned unsaturated polycarboxylic acid Free carboxyl group-containing esters such as dibutyl ester; Free carboxyl group-containing nitriles such as mononitriles of unsaturated polycarboxylic acids, non-polymerizable polyvalent carboxyl group-containing nitriles such as phthalic acid, succinic acid, adipic acid , Phthalic acid,
Examples include free carboxyl group-containing esters such as monoesters of non-polymerizable polycarboxylic acids such as succinic acid and adipic acid with allyl alcohol, and hydroxyl group-containing unsaturated compounds such as 2-hydroxyethyl (meth) acrylate. it can.

The copolymer (A) can be produced as a particulate copolymer by an emulsion polymerization method or a suspension polymerization method using a radical initiator. From the viewpoints of particle size and particle size uniformity, it is desirable to use the emulsion polymerization method. The total amount of each monomer or polymerization agent such as a radical initiator may be added at the start of the reaction, or may be added after the start of the reaction in any desired amount. The polymerization is carried out in a reactor from which oxygen has been removed at 0 to 80 ° C, but operating conditions such as temperature and stirring may be arbitrarily changed during the reaction. The polymerization method may be either continuous or batch.

Examples of the radical initiator include organic peroxides such as benzoin peroxide, cumene hydroperoxide, paramenthane hydroperoxide and lauroyl peroxide, diazo compounds represented by azobisisobutyronitonil, and potassium persulfate. A redox catalyst represented by a combination of an inorganic compound and an organic compound-iron sulfate is used.

The thermoplastic block-like copolymer (B) is a thermoplastic non-elastomeric copolymer block mainly composed of a hard segment and a soft segment, and the hard segment has a glass transition point of 20 ° C. or higher.
The soft segment is a block-shaped copolymer made of an elastomeric polymer having a glass transition point of 10 ° C. or lower.

The hard segment constituting the block copolymer is characterized by being a thermoplastic non-elastomeric polymer block having a glass transition point of 20 ° C. or higher. A vinyl aromatic compound is mentioned as a preferable example of the monomer component which mainly comprises this polymer block.
Specifically, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyl pyridine and the like, particularly styrene, α
-Methylstyrene is preferred. The hard segment constituting the block copolymer is, if necessary, copolymerized with the vinyl aromatic compound and a conjugated diene compound or other copolymerizable monomer component within the above glass transition point region. Can also be obtained by performing.

Further, the soft segment constituting the block copolymer is characterized by being an elastomeric polymer block having a glass transition point of 10 ° C. or lower. A conjugated diene compound is mentioned as a preferable example of the monomer component which mainly comprises this polymer block. Specifically, 1.3-butadiene, isoprene, 2,3-dimethyl-1,
3-butadiene, 1,3-pentadiene, 2-methyl-1,3
-Pentadiene, 1,3-hexadiene, 4,5-diethyl-
1,3-octadiene, 3-butyl-1,3-octadiene,
Examples include chloroprene, which are industrially available,
Further, in order to obtain a polymer block having excellent physical properties, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are more preferable. The soft segment constituting the block-shaped copolymer, if necessary, within the above glass transition point region,
It can also be obtained by copolymerizing the conjugated diene compound with a vinyl aromatic compound or other copolymerizable monomer component.

An ethylenically unsaturated monomer is used as the photopolymerizable unsaturated monomer (C). The photopolymerizable ethylenically unsaturated monomer imparts higher water resistance to the printing plate. Examples of such a monomer include a compound having an ethylenically unsaturated group, and preferably a polyfunctional monomer is included. The use of the polyfunctional monomer in the resin system of the present invention imparts water resistance to the printing plate, but does not hinder the developability of the resin plate to water. Examples of the monomer include the above-mentioned monomer used in the synthesis of core / shell three-dimensional crosslinked polymer particles, a polyfunctional monomer having good compatibility with a resin system (for example, those in the following specific examples, or US Pat. No. 3,801,328) may be used.

Specific examples of the monomer include unsaturated carboxylic acid ester (for example, n-butyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, lauryl (meth)
Acrylate, stearyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di
(Meth) acrylate, polyethylene glycol di (meth)
Acrylate, methoxy polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, diallyl itaconate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,3
-Propylene glycol di (meth) acrylate, 1,4-
Cyclohexanediol di (meth) acrylate, 1,2,4
-Butanetriol tri (meth) acrylate, glycerol polypropylene glycol tri (meth) acrylate, 1,4-benzenediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,5 -Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc., unsaturated amides (e.g., methylenebis (meth) acrylamide, ethylenebis
(Meth) acrylamide, 1,6-hexamethylenebis (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, N- (hydroxymethyl) acrylamide, N- (hydroxymethyl) methacrylamide, N-
(β-hydroxyethyl) acrylamide, N- (β-hydroxyethyl) methacrylamide, N, N-bis (β-hydroxyethyl) acrylamide, N, N-bis (β-hydroxyethyl) methacrylamide), divinyl ester
(For example, divinyl adipate, divinyl phthalate, etc.), acrylated or methacrylated urethane (these are derived from, for example, a hydroxyalkyl acrylate or hydroxyalkyl methacrylate and an isocyanate compound), a diacrylic or dimethacrylic ester, or an aromatic compound and a polyalcohol. (For example, diepoxy polyether derived from bisphenol or novolac compound), polyester mono / di (meth) acrylate, polyether mono / di (meth) acrylate and the like are also included. One or more of these compounds may be used, with water-soluble or water-dispersible monomers being generally preferred.

Examples of the photopolymerizable initiator (D) include benzoin ethers (eg, benzoin isopropyl ether, benzoin isobutyl ether), benzophenones (eg, benzophenone, methyl-o-benzoin benzoate, 4,4′-bis). (Dimethylamino) -benzophenone), xanthones (for example, xanthone, thioxanthone, 2-chlorothioxanthone), acetophenone (for example, acetophenone, trichloroacetophenone, 2,2
-Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone), benzyl, 2-ethylanthraquinone, methylbenzoyl formate, 2-hydroxy-2-methylpropionphenone, 2-hydroxy-2
-Methyl-4'-isopropyl-isopropiophenone,
Examples thereof include 1-hydroxycyclohexyl phenyl ketone. These may be used alone or in combination.

The photosensitive resin composition used in the present invention is formed by containing the above-mentioned components (A) to (D). Usually, a basic nitrogen-containing compound (E) is added to this component. To be done. This compound (E) further improves the water developability. The basic nitrogen-containing compound (E) may be blended in the photosensitive resin composition as described above, or may be blended in the aqueous developer described later. Moreover, you may mix | blend with both.

The basic nitrogen atom-containing compound (E) is preferably a compound containing a tertiary basic nitrogen atom and a vinyl group. Generally, the nitrogen atom-containing compound has the following formula:

[0034]

Embedded image

[0035]

Embedded image

Can be represented by Preferred compounds have the formula (II
Except for the case where Y is H in I), the above formula (II) or
It is a compound represented by (III). Among such compounds, suitable examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl-N '-( Examples thereof include (meth) acryloyl carbamate and N, N-diethylaminoethoxyethyl (meth) acrylate. Further, N, N-dimethylaminoethoxyethanol and N, N-diethylaminoethoxyethanol are also preferably used. These may be used as a mixture. Other non-photopolymerizable amine compounds such as 2-N-morphoethanol and 2-piperidinoethanol may be used in combination with the above compounds (II) (III) and have a boiling point of 5
A monoamine, diamine or triamine compound having a temperature of 0 ° C. or higher is also used.

The photosensitive resin composition of the present invention may further contain a conventional additive, for example, 0.001% to 2.0% by weight of a thermal addition polymerization inhibitor based on the weight of the total photosensitive resin composition without a solvent. Can be made. Suitable inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p-t
-Butylcatechol, 2,6-di-t-butyl-p-cresol, benzoquinone, 2,5-diphenyl-p-benzoquinone, p-methoxyphenol, tertiary butylpyrocatechol, pyrogallol, β-naphthol, 2, 6-ditertiary butyl-p-cresol, phenothiazine, pyridine,
Nitrobenzene, Dinitrobenzene, British Patent No. 1,453,
And bis (substituted amino) sulfides disclosed in US Pat. No. 4,168,981. Other useful inhibitors include p-toluquinone, chloranil and thiazine dyes such as thionine blue G (CI 52025), methylene blue B (CI
52015) and toluidine blue (CI52040). Such compositions can be photopolymerized without removing the inhibitor. Preferred inhibitors are 2,6-ditertiary butyl-4-methylphenol and p-methoxyphenol.

The photosensitive resin composition of the present invention is further mixed with an appropriate amount of a well-known compatible antioxidant and / or antiozonant to prevent polymerization inhibition by oxygen and ozone. Can be improved. Antioxidants useful in the present invention include alkylated phenols (eg, 2,6-ditertiarybutyl-p-cresol), alkylated bisphenols (eg, 2,2-methylenebis (4-methyl-6-). Tertiary butylphenol)),
1,3,5-Trimethyl-2,4,6-tris- (3,5-ditertiary butyl-4-hydroxybenzyl) benzene, 2-4-hydroxy-3,5-ditertiary butylanilino- Mention may be made of 4,6-bis (n-octylthio) -1,3,5-triazine, polymerized trimethyldihydroquinone and dilaurylthiodipropionate. As antiozonants useful in the present invention, microcrystalline wax and paraffin wax, dibutylthiourea, 1,1,3,3-tetramethyl-2-thiourea, "antithiozonant" AFD (Nafton product) , Norbornene,
(For example, di-5-norbornene-2-methyladipate,
Di-5-norbornene-2-methyl maleate, di-5-
Norbornene-2-methyl terephthalate), "Ozone protector" 80 (manufactured by Reinhold Chemical Co.), N-phenyl-2-naphthylamine, unsaturated vegetable oils (e.g. rapeseed oil, linseed oil, safflower oil), polymers and resin
(For example, ethylene / vinyl acetate copolymer resin,
Chlorinated polyethylene, chlorosulfonated polyethylene,
Chlorinated ethylene / methacrylic acid copolymer, polyurethane, polypentadiene, polybutadiene, furfural derived resin, ethylene / propylene / diene rubber, diethylene glycol ester of rosin and α-methylstyrene / vinyltoluene copolymer).

If desired, the photosensitive resin composition also comprises a non-mild polymeric or non-polymeric material which is essentially transparent at the wavelengths used to expose the photosensitive resin material and which does not scatter actinic radiation. Contains coalescing organic or inorganic fillers or reinforcing agents, such as polystyrene, internal three-dimensionalized fine resin particles (microgels), organophilic silica, bentonite, silica, powdered glass, colloidal carbon and various types of dyes and pigments Can be made.
Such materials are used in various amounts depending on the desired properties of the elastomeric composition. Fillers improve the strength of the elastic layer, reduce tack (stickiness), and are also useful as colorants.

It is also necessary to optionally use a plasticizer having good compatibility with the photosensitive resin layer to lower the glass transition point of the binder and facilitate the selective phenomenon. Among the common plasticizers which may be used are maleic acid esters (e.g. dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, diallyl maleate, monomethyl maleate). , Monobutyl maleate, maleic acid-mono-2-ethylhexyl), fumaric acid ester (for example, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, diisobutyl fumarate, di-s-butyl fumarate, Fumaric acid-di-2-ethylhexyl), itaconic acid ester (for example, dimethyl itaconic acid, dibutyl itaconic acid, itaconic acid-di-2-ethylhexyl, monomethyl itaconic acid, monobutyl itaconic acid), phosphoric acid ester (for example,
Tributyl phosphate, phosphoric acid-tri-2-ethylhexyl), aliphatic dibasic acid ester (for example, dibutyl adipate, adipic acid-di-n-hexyl, adipic acid-di-2)
-Ethylhexyl, azelaic acid-di-2-ethylhexyl, dibutyl sebacate, sebacic acid-di-2-ethylhexyl).

The photosensitive resin composition of the present invention is prepared by pre-kneading the crosslinked particle copolymer (A) and the thermoplastic block copolymer (B), and then adding the basic nitrogen atom-containing compound (E) and the photopolymerizable compound. A mixture of the unsaturated monomer (C) and the photopolymerization initiator (D) was sequentially added,
It is obtained by kneading.

The blending ratio of each of the components (A) to (E) is 10 to 90% by weight, preferably 25 to 80% by weight, of the crosslinked particle copolymer (A), and the thermoplastic block copolymer (B). Is 10 to 80% by weight, preferably 15 to 70% by weight, the basic nitrogen atom-containing compound (E)
Is 1 to 30% by weight, preferably 2 to 20% by weight, the photopolymerizable unsaturated monomer (C) is 1 to 60% by weight, preferably 3 to 40% by weight,
The photopolymerization initiator (D) is 0.01 to 10% by weight, preferably 0.05 to
5% by weight.

When the content of the crosslinked particle copolymer (A) is less than 10% by weight, satisfactory developability with an aqueous developer cannot be obtained. On the other hand, if it exceeds 90% by weight, the photosensitive resin has a poor film forming property and adversely affects the film strength after image formation. When the thermoplastic block copolymer (B) is less than 10% by weight, the film strength after image formation becomes weak, and when it exceeds 80% by weight, the water developability and the printing plate material obtained after water development are It adversely affects the image quality. Basic nitrogen atom-containing compound
When (E) is less than 1% by weight, the water developability is poor, and 3
If it exceeds 0% by weight, the water resistance of the plate material becomes poor. When the photopolymerizable unsaturated monomer (C) is less than 1% by weight, the product is not sufficiently cured, and when it exceeds 60% by weight, the quality formation as a solid plate is adversely affected. Photopolymerization initiator (D)
If less than 0.01% by weight, sufficient photosensitivity cannot be obtained,
If it exceeds 5% by weight, the image quality of the printing plate material obtained after water development is adversely affected. The preparation of the photosensitive resin composition of the present invention is not particularly limited, and for example, each of the above components (A), (B),
It is obtained by uniformly mixing (C), (D) and (E).

The kneading is usually carried out while heating, using, for example, a roll tester, a pressure kneader, an intermixer, etc.
(A) to (E) and other additives are added, and the mixture is kneaded for 25 to 90 minutes to obtain the photosensitive resin composition of the present invention.

In the present invention, the water-developable photosensitive resin composition is exposed through a negative film to cure the exposed portion,
The unexposed area is developed with a developing solution. Of course, the resin composition is formed as a layer on a suitable base material. Examples of substrates include plastic plates, plastic sheets, metal plates and metal sheets.

In the present invention, when the exposed photosensitive resin composition is developed with an aqueous developer, the aqueous developer contains water and a nonionic surfactant.

The water used for the above developing solution is of German hardness (1 ° d
= 17.85 ppm / CaCO ₃ ) is 20 ° or less, preferably 10 ° or less. When hard water with a German hardness of 20 ° or more is used, the polyvalent metal ion (divalent or more metal ion) contained in the water and the functional group of the hydrophilic crosslinked particle which is a component of the photosensitive resin composition are ionic. Crosslinking occurs and the hydrophilic crosslinked resin particle layer cannot be dispersed in water, resulting in poor development. In the case of using a material having a German hardness of more than 20 ° as described above, it is necessary to soften the water by using ion exchange, a water softening agent, a water softening device or the like. Examples of the water softener include sodium ethyleneamine tetraacetate, sodium nitrilotriacetate, sodium citrate, sodium tripolyphosphate and the like. Water also has a pH of 5 or higher, preferably pH 7-9. If the pH of water is less than 5, it becomes difficult to neutralize the functional groups of the hydrophilic crosslinked resin particles with the alkaline compound, resulting in poor development. Water also preferably has an electrical conductivity of less than 1.5 mS / cm,
It preferably has 1 mS / cm or less. The electrical conductivity of water
If it exceeds 1.5 mS / cm, the permeability of water molecules into the hydrophilic crosslinked particle layer is lowered due to the presence of other ions contained in water, resulting in poor development.

The nonionic surfactant is used because it is not affected by acids and alkalis as a chemical substance and has high hard water resistance. Examples of the nonionic surfactant used in the present invention include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, and other polyoxyethylene alkyls. Ethers; polyoxyethylene alkylphenyl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether; polyoxyethylene polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene cetyl ether, etc. Polyoxyethylene polyoxypropylene alkyl ethers; Polyoxyethylene polyoxypropylene block polymers S; polyoxyethylene polyoxypropylene glycols;
Polyoxyethylene glycol monolaurate, polyoxyethylene glycol monostearate, polyoxyethylene glycol monooleate, polyoxyethylene glycol dilaurate, polyoxyethylene glycol distearate, polyoxyethylene glycol dioleate, polyoxyethylene glycol lanolin fatty acid Esters, polyoxyethylene fatty acid esters such as polyoxyethylene glycol monopalmitate; polyoxysorbitan monolaurate, polyoxysorbitan monopalmitate, polyoxysorbitan monostearate, polyoxysorbitan tristearate, polyoxysorbitan Polyoxyethylene polyhydric alcohol fatty acid partial esters such as triolate; sorbitan monolaurate, sorby Tandem monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan tristearate, and other polyhydric alcohol fatty acid partial esters; polyglycerin fatty acid esters; polyoxyethylene castor oil and poly Oxyethylene hydrogenated castor oil; diethanolamine such as lauric acid monoethanolamide, stearic acid monoethanolamide, coconut oil fatty acid monoethanolamide, lauric acid diethanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamide, monoethanolamine, isopropanol Fatty acid alkanolamides, which are condensation products of amines and fatty acids; ethylene oxide addition polymerization to fatty acid amides, Polyoxyethylene fatty acid amides obtained by dehydration condensation of ethylene glycol; polyoxyethylene alkyl amines, polyoxyethylene lauryl amine, alkyl amine oxides; and the like.

Of the nonionic surfactants used in the present invention, those excluding nonionic surfactants containing propylene oxide, butylene oxide, or nitrogen or sulfur have an HLB (hydrophilic-lipophilic balance) range of 8. ~ 1
8, preferably 10-14. Surfactants outside this range can degrade image quality. HLB can be calculated from the three formulas proposed by Glibin.

(1) In the case of polyhydric alcohol fatty acid ester HLB = 20 (1-S / A) (In the formula, S is saponification value of ester and A is neutralization value of fatty acid.) (2) Many In the case of a polyhydric alcohol ester derivative HLB = (E + P) / 5 (wherein E represents the oxyethylene content (%) and P represents the polyhydric alcohol content (%).) (3) The hydrophilic group is oxy In case of containing only ethylene group HLB = E / 5 (In the formula, E represents oxyethylene content (%).)

The amount of nonionic surfactant added to water is 0.01.
-15% by weight, preferably 0.01-10% by weight. If it is less than 0.01% by weight, there is no effect of the addition of the nonionic surfactant, and if it exceeds 15% by weight, it can be added, but an increase in the effect with respect to the addition amount cannot be expected.

The aqueous developer used in the present invention basically comprises water and a nonionic surfactant as described above. The pH of the developer as a whole is preferably 6-11. This is from the viewpoint of safe handling of workers. The electric conductivity of the developer is 1.5 mS / cm or less. If the electric conductivity exceeds 1.5 mS / cm, defective development may occur.

In addition to the nonionic surface active agent, other surface active agents such as cationic surface active agents, anionic surface active agents and zwitterionic surface active agents may be added to the developer. . Of course, the addition of these surfactants in a small amount should not deteriorate the performance of the aqueous developer.

As the anionic surfactant, aliphatic carboxylic acid salts such as sodium laurate, sodium myristate, sodium palmitate, sodium stearate, sodium oleate, etc .; resins such as sodium abietic acid, sodium rosinate, etc. Soaps; N-acyl-N-methylglycine soda, N-acyl-N-methyl-β-alanine soda, N
-N-acyl amino acid salts such as sodium acylglutamate, alkyl ether carboxylates; primary and secondary alkyl sulfates such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene sodium lauryl ether sulfate, polyoxyethylene Primary and secondary polyoxyethylene alkyl ether sulfates such as lauryl ether sulfate triethanolamine; alkylbenzene sulfonates such as sodium lauryl benzene sulfonate and sodium stearyl benzene sulfonate; sodium propylnaphthalene sulfonate, butyl naphthalene sulfonate Alkylnaphthalene sulfonates such as soda; Polyoxyethylene lauryl phenyl ether sulfonates Polyoxyethylene alkyl phenyl ether sulfonates such as soda; Sulfated oils such as sulfated castor oil, sulfated beef oil, etc .; Sulfated fatty acid esters such as sulfated butyl oleate; Dioctylsulfosuccinic acid sodium salt; Dialkylsulfosuccinic acid ester salts, α -Olefin sulfonates, hydroxyalkane sulfonates; N-methyl-
N-alkyl taurine salts; N-alkyl sulfosuccinic acid monoamide salts; fatty acid monoglyceride sulfuric acid ester salts; alkyl diphenyl ether disulfonic acid salts; lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester soda salt, etc. Salts; polyoxyethylene lauryl ether phosphate monoester disodium salt, polyoxyethylene lauryl ether phosphate diester soda salt, and other polyoxyethylene alkyl phosphate salts; naphthalene sulfonate formalin condensates; melamine sulfonate formalin Styrene such as polycondensate
Salts of partially saponified maleic anhydride copolymer; Salts of partially saponified olefin-maleic anhydride copolymer;

Examples of the carbon compounds containing -SO ₃ N group and having 11 or less carbon atoms are sodium benzene sulfonate, sodium naphthalene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, sodium mesitylene sulfonate,
Sodium styrene sulfonate, sodium chlorobenzene sulfonate, sodium nitrobenzene sulfonate, sodium acetamide benzene sulfonate, disodium phenol-2,4-disulfonate, sodium 4-nitrotoluene-2-sulfonate, sodium naphthol sulfonate, sodium pyridine sulfonate , Sodium methylsulfonate, sodium ethylsulfonate, sodium propanesulfonate, sodium butanesulfonate, sodium pentanesulfonate, sodium hexanesulfonate, sodium heptanesulfonate, sodium octanesulfonate, sodium cyclohexanesulfonate,
Examples thereof include sulfonates such as sodium 2-bromoethanesulfonate and sodium 2-methylpropane-1-sulfonate; salts of alkyl sulfates. Although sodium salt is mainly mentioned as a specific example, potassium salt, ammonium salt, magnesium salt, calcium salt and the like are also possible and are not particularly limited thereto.

As the cationic surfactant, primary, secondary and tertiary amine salts such as monostearyl ammonium chloride, distearyl ammonium chloride and tristearyl ammonium chloride; stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl Quaternary ammonium salts such as benzyl ammonium chloride; N-
Alkylpyridinium salts such as cetylpyridinium chloride and N-stearylpyridinium chloride; N, N
Dialkylmorpholinium salts; Aliphatic amide salts of polyethylene polyamines; Acetates of urea compounds of amides of aminoethylethanolamine and stearic acid; 2
-Alkyl-1-alkyl-1-hydroxyethyl imidazolinium chloride benzalkonium salt; benzethonium chloride; and the like. In addition, chloride was mainly mentioned as a specific example, but bromide, alkyl sulfate, acetate, etc. are also possible and are not particularly limited thereto.

Examples of the amphoteric surfactant include amino acid type amphoteric surfactants such as sodium laurylaminopropionate;
Carboxybetaine-type amphoteric surfactants such as lauryldimethyl betaine and lauryldihydroxyethyl betaine; Sulfobetaine-type amphoteric surfactants such as stearyl dimethylsulfoethylene ammonium ethylene ammonium betaine; Imidazolinium betaine-type amphoteric surfactants; Lecithin Etc.

As mentioned above, the basic nitrogen atom-containing compound (E) may be added to the above-mentioned aqueous developer. Examples of such include those mentioned above, but in addition,
In addition to ammonia, it is composed of an organic compound having one or more primary to tertiary amino groups.

Examples of the organic compound having one or more primary to tertiary amino groups include primary amines such as methylamine, ethylamine, propylamine and butylamine; dimethylamine, methylethylamine, diethylamine and methyl. Secondary amines such as propylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine; and as tertiary amines, trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylpropylamine, Methylethylpropylamine, diethylpropylamine, methyldipropylamine, ethyldipropylamine, tripropylamine, dimethylbutylamine, methyldibutylamine, methyl ether Tributylamine, diethylbutylamine, ethyldibutylamine, methylpropylbutylamine, ethylpropylbutylamine, dipropylbutylamine, propyldibutylamine, tributylamine, and other trialkylamines, dimethylethanolamine, methyldiethanolamine, diethylethanolamine, ethyldiethanolamine, and the like. Alkylalkanol tertiary amines, triethanolamine, diethanolpropanolamine, ethanoldipropanolamine, trialkanolamines such as tripropanolamine, N, N-dimethylaminoethoxyethanol,
N, N-dialkylaminoalkoxy alkanols such as N, N-diethylaminoethoxyethanol, N, N-dimethylaminoethoxypropanol, N, N-diethylaminoethoxypropanol, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, dipropylaminoethyl
(Meth) acrylate, N, N-dimethylaminopropyl
(Meth) acrylate, N, N-diethylaminopropyl
N, N-dialkylaminoalkyl (meth) acrylates such as (meth) acrylate, N, N-dipropylaminopropyl (meth) acrylate, N, N-dimethylaminoethoxyethyl (meth) acrylate, N, N-diethylamino N, N- such as ethoxyethyl (meth) acrylate
Dialkylaminoalkoxyalkyl (meth) acrylates, N- (N ', N'-dimethylaminoethyl) (meth) acrylamide, N- (N', N'-diethylaminoethyl)
(Meth) acrylamide, N- (N ', N'-dimethylaminopropyl) (meth) acrylamide, N- (N', N'-diethylaminopropyl) (meth) acrylamide, etc. Examples thereof include tertiary amino group-containing carbamates such as acrylamides, N, N-dimethylaminoethyl-N '-(meth) acryloyl carbamate and N, N-diethylaminoethyl-N'-(meth) acryloyl carbamate. it can. These amino group-containing compounds can be used alone or in combination of two or more.

As described above, in order to control the pH of the developer, other alkaline compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium thiosulfate, sodium sulfite, Inorganic salt compounds such as calcium carbonate, sodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium bicarbonate;
Sodium acetate, sodium citrate, monosodium succinate, sodium fumarate, sodium benzoate, sodium polyacrylate,
Salts of organic acids such as calcium actylate and calcium naphthenate may be added.

[0061]

By using the developing method of the present invention,
When a specific water-developable photosensitive resin composition is used, its developability is greatly improved, and all other properties, that is, the properties useful as a flexographic printing plate are retained.

[0062]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The production examples of the photosensitive resin composition, the method for preparing the photosensitive resin plate material, and the method for evaluating the plate quality of the photosensitive resin plate material are shown below.

Production Example of Photosensitive Resin Composition (a) Preparation of Hydrophilic Crosslinked Resin Particles Polymerization was carried out at 30 ° C. in an autoclave having an internal volume of 20 liters using the following components. Ingredients Weight part Butadiene 69 Methacrylic acid 9 Divinylbenzene 2 Methylmethacrylate 20 Potassium persulfate 0.27 t-Dodecyl mercaptan 0.6 Cyanoethylated diethanolamine 0.15 Sodium dodecylbenzenesulfonate 5 Potassium hydroxide 0.11 Water 250 Polymerization Of the above ingredients, the charge amount of methacrylic acid is 6
Weight part and divinylbenzene charge amount to 1 part,
All the other components were charged and started, and when the polymerization conversion rate reached 60%, 3 parts by weight of methacrylic acid and 1 part by weight of divinylbenzene were added to continue the polymerization. The total composition (mol%) of the monomers was butadiene / methacrylic acid / divinylbenzene / methyl methacrylate = 80/7/1/12.

Thereafter, when the conversion of polymerization reached 90%, 0.2 part by weight of hydroxylamine sulfate was added to 100 parts by weight of all the monomers to terminate the polymerization. Then
Steam distillation was performed under heating to remove residual monomers, and an aqueous emulsion dispersion was obtained. The average particle size was 71 nm.
The resulting latex is salted out with calcium chloride,
By washing with water and drying, a crumb-shaped carboxyl group-containing crosslinked particle copolymer (A-1) was obtained.

The resulting hydrophilic crosslinked resin particles (A-1) 100
Based on parts by weight, 43 parts of a styrene-isoprene-styrene type thermoplastic block copolymer (B) (Diar Shell Elastomer Co., Ltd.), 20 parts of maleic acid half-ester modified isoprene polymer (Kuraray Co., Ltd.) Was kneaded for 10 minutes using a roll tester whose temperature was controlled at 110 ° C.
Then, as a photopolymerizable unsaturated monomer (C), 30 parts by weight of lauryl methacrylate and 10 parts by weight of 1,6-hexanediol dimethacrylate, 10 parts by weight of 1,6-hexanediol diacrylate, a photopolymerization initiator ( As E), a mixture of 1 part by weight of 2,2-dimethoxyphenylacetophenone and 0.5 part by weight of t-butylcatechol as a storage stabilizer was gradually added to the pre-kneaded product and kneaded for 40 minutes to prepare a photosensitive resin composition.
(a) was obtained.

Production Example of Photosensitive Resin Composition (b) 100 parts by weight of the hydrophilic cross-linked resin particles (A-1) are added to a styrene-isoprene-styrene type thermoplastic block copolymer (B) (JS. Shell Elastomer Co., Ltd. 43
Part with a roll tester whose temperature is controlled at 110 ° C.
Kneaded for 0 minutes. Then, as a photopolymerizable unsaturated monomer (C), 20 parts by weight of N- (2-dimethylaminopropyl) methacrylamide, 30 parts by weight of lauryl methacrylate and
1,6-hexanediol dimethacrylate 10 parts by weight, 1,6
A mixture of 10 parts by weight of hexanediol diacrylate, 1 part by weight of 2,2-dimethoxyphenylacetophenone as a photopolymerization initiator (E), and 0.5 parts by weight of t-butylcatechol as a storage stabilizer was gradually added to the pre-kneaded product. In addition, the mixture was kneaded for 40 minutes to obtain a photosensitive resin composition (b).

[0067] Production Example monomer component of the photosensitive resin composition (c), butadiene / .omega. Karubokishiji (pentamethylene carboxy) oxy acrylate / divinylbenzene / styrene = 88/5/1/6 molar ratio , By carrying out emulsion polymerization, hydrophilic crosslinked resin particles (A-2)
A photosensitive resin composition (c) was obtained by using the same components as in Production Example (b) and following the same procedure except that the above was prepared.

[0068] Production Example monomer component of the photosensitive resin composition (d), the molar ratio of butadiene / methacrylic acid / methyl methacrylate = 81/7/12, by performing the emulsion polymerization, a hydrophilic non-crosslinked resin A photosensitive resin composition (d) was obtained by using the same components as in Production Example (b) and following the same procedure except that the above was prepared.

Method for preparing photosensitive resin plate material The obtained photosensitive resin composition was preliminarily coated with a polyethylene terephthalate film (PET) and a chloroprene adhesive (trade name: HIBON 1920LT Hitachi Chemical Co., Ltd.) in a thickness of 5 μm. A 1.7 mm-thick photosensitive resin plate material was produced on the coated PET by a scissor press and a roll molding machine.

Example The entire surface of the PET coated with the adhesive of the photosensitive resin plate material obtained as described above was exposed to the exposure device JE-A manufactured by JEOL Ltd.
2-SS type is used, and it is exposed for a predetermined time by a 3 mW / cm ² ultraviolet fluorescent lamp (back exposure). Next, the P of the back unexposed surface
The ET film is peeled off, a negative film having an appropriate image is brought into uniform contact under a vacuum condition, and the film is exposed for 10 minutes by the same exposure machine (main exposure). After that, in each water-based developer shown in Table 1 using a JEOL Seiki Co., Ltd. eluator JW-A2-PD type, brushing with a nylon brush was performed at 40 ° C, followed by drying at 80 ° C for 10 minutes and the same exposure. Exposure for 5 minutes on the machine
(Post-exposure) and image formation was performed. Table 1 shows the results.

[0071]

[Table 1]

Evaluation content and evaluation method Evaluation of water development rate A photosensitive resin plate material was used as JW-A2-PD manufactured by JEOL Ltd.
Using a mold developing machine, in each aqueous developer shown in Table 1, brushing was performed with a nylon brush at 40 ° C., the time required until the photosensitive resin layer disappeared was measured, and the elution rate was calculated.

Evaluation of image quality Image quality is evaluated by dot reproducibility, minimum thin line remaining property, outline depth, and dot depth by a non-contact depth measuring device (Union Optical Co., Ltd.).
Evaluation was performed using a micro two-dimensional measuring machine (Eunotech Co., Ltd.). -Reproducibility of halftone dots The reproducibility of a negative film on a plate for 85% 3% halftone dots was evaluated. The judgment criteria are shown below. A: 85 lines 3% halftone dots faithfully reproduce 100%. B: 85 lines Part of 3% halftone dots are worn or chipped. C: 85 lines 50% or more of 3% halftone dots do not remain.・ Minimum fine line persistence Convex line width of negative film, 0.20, 0.15, 0.10, 0.05, 0.02
In mm, the minimum convex line width that is faithfully reproduced without scratches or chips was evaluated. -Outline depth Depth with a dot diameter of 750μ and 250μ was measured at 5 points and the average value was shown.・ Dotted depth The depth of 85-dot 65% halftone dot was measured at 5 points and the average value was shown. -Electrical conductivity The electrical conductivity of each aqueous developer was measured using CM-11P manufactured by Toa Denpa Kogyo Co., Ltd.

[Brief description of drawings]

FIG. 1 is a schematic view showing a developing method disclosed in Japanese Patent Publication No. 5-6178.

[Explanation of symbols]

1 ... Base material, 2 ... Photosensitive resin layer, 3 ... Negative film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03F 7/033 G03F 7/033

Claims (8)

[Claims] 1. A method for developing a water-developable photosensitive resin composition, comprising exposing an unexposed portion by developing with an aqueous developer after exposing the water-developable photosensitive resin composition in an image form. A resin composition containing (A) 10 to 95 mol% of an aliphatic conjugated diene monomer, one or more kinds of functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group and a phosphoric acid group .1-30
Mol%, 0.1 to 20 mol% of monomers having two or more addition-polymerizable groups, excluding aliphatic conjugated diene monomers, and 0 to 70 mol% of other copolymerizable monomers. However, a hydrophilic crosslinked particle copolymer obtained by polymerizing a monomer mixture in which +++ = 100 mol%, (B) a thermoplastic non-elastomeric block X having a glass transition point of 20 ° C. or higher is 1 to 40 mol%. And a thermoplastic block copolymer containing 60 to 99 mol% of an elastomer Y having a glass transition point of 10 ° C. or lower and having an XY-X type structure or an XY type structure, (C) photopolymerizable A method for developing a water-developable photosensitive resin composition, which contains an unsaturated monomer and (D) a photopolymerization initiator, and the aqueous developer contains water and a nonionic surfactant. . 2. The developing method according to claim 1, wherein the basic nitrogen-containing compound (E) is blended in either or both of the water-developable photosensitive resin composition and the aqueous developer. 3. The basic nitrogen-containing compound (E) has the formula: Or The developing method according to claim 2, represented by 4. Water has a German hardness (1 ° d = 17.85 ppm / Ca).
The developing method according to claim 1, wherein CO ₃ ) is 20 ° or less. 5. The developing method according to claim 1, wherein the water has a pH of 5 or more. 6. The developing method according to claim 1, wherein the water has an electric conductivity of less than 1.5 mS / cm. 7. The developing method according to claim 1, wherein the nonionic surfactant is HLB 8-18. 8. The developing method according to claim 1, wherein the amount of the nonionic surfactant added to the aqueous developer is 0.01 to 15% by weight.