JP2000250206A - Photopolymerizable composition and photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high sensitivity photopolymerizable composition having good developability and free from problem on handling such as a foul odor by incorporating an addition polymerizable compound having an ethylenically unsaturated double bond, a radical activator, a sensitizing dye and an aliphatic amino acid salt and using a pyromethene borate dye as the sensitizing dye. SOLUTION: The photopolymerizable composition contains an addition polymerizable compound having an ethylenically unsaturated double bond, a radical activator, a sensitizing dye and an aliphatic amino acid salt and a pyromethene borate dye is contained as the sensitizing dye. The pyromethene borate dye may be a dye having a structure of the formula, wherein R1-R6 are each H, halogen, alkyl, aryl or the like, R7 is H, alkyl, aryl or aralkyl, X1 and X2 are each halogen, alkyl, aryl, aralkyl or the like and H atoms of the groups R1-R7 may further be substituted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is suitable for forming various patterns such as photosensitive lithographic printing plates, copper etching resists for wiring boards, copper etching resists for gravure, dry films, color filters and pigment dispersion resists for plasma displays. The present invention relates to a photopolymerizable composition that can be used, and particularly to a highly sensitive photopolymerizable composition.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiation system, and an organic polymer binder used as desired is further coated on a support to form a photopolymerizable composition. A method of forming a cured relief image by exposing a light-sensitive material provided with a layer of an object to polymerize and cure an exposed portion and dissolving and removing an unexposed portion, a method in which at least one is transparent between two substrates. A method of forming an image by providing a layer of a polymerizable composition, exposing from the transparent support side to cause a change in adhesive strength by light, and peeling off the support, and other toner adhesion of the photopolymerizable composition layer by light There is an image creation method utilizing a change in gender.

In recent years, high-sensitivity photosensitive materials using a photopolymerizable photosensitive material have been studied in various application fields. Among these, there is a laser direct plate making as a system which is expected to be practically used, and a high sensitivity photopolymer system corresponding to exposure with a laser oscillation wavelength, for example, 488 nm of an argon ion laser and 532 nm of an FD-YAG laser. Development is desired and various proposals have been made.

[0004] The biggest problem in these is how to improve the sensitivity of a light-sensitive material to light rays. It is well known that the ability of the photopolymerization initiation system to generate active radicals rapidly decreases sensitivity to light rays of 450 nm or more. Various proposals have heretofore been made with respect to a photopolymerization composition containing a photopolymerization initiation system capable of responding to light in the visible light region. Among them, a system of a pyromethene complex sensitizer and a radical generator which is extremely sensitive to the wavelength around the FD-YAG laser and is particularly effective as a sensitizer for the FD-YAG laser (Japanese Patent Laid-Open No. 7-5885). 4-241338, 6-07184, 6-141588, 6-211
271, 7-22547, 8-0626218, 8
333455, 9-989572 and the like).

It is well known that a radical generator and a sensitizer are used in combination as a photopolymerization initiation system. A system containing titanocenes and an aromatic amino acid ester such as ethyl diethylaminobenzoate is disclosed in Japanese Patent Laid-Open Publication No. No. 301208 and the like. Further, Japanese Patent Application Laid-Open No. 9-503871, Japanese Patent Application Laid-Open No. 8-254821, and Japanese Patent Application Laid-Open No. 5-13
No. 2507 and the like, a system containing titanocenes and N-phenylglycine or a derivative having a specific structure thereof,
JP-A-10-246954 describes a photopolymerizable composition containing a titanocene, a merocyanine dye or a benzopyran dye, and an amino acid salt such as an N-phenylglycine salt.

However, all of these photopolymerizable compositions have a photosensitive wavelength range up to the visible light range, but have insufficient sensitivity. For example, a low-output argon laser or FD-Y
When an image is recorded at a high speed by an AG laser, it is necessary to prepare a composition having higher sensitivity. When N-phenylglycine was used, odor became a problem.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has a high developing property, has no problem in handling such as odor, and has a high sensitivity. The purpose is to provide things.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and used a combination of a radical activator, an aliphatic amino acid salt and a dye having a specific structure as a photopolymerization initiation system. In this case, it was found that the sensitivity was greatly improved and the odor during drying was suppressed, and the present invention was reached. That is, the gist of the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond,
A photopolymerizable composition containing a radical activator, a sensitizing dye and an aliphatic amino acid salt, wherein the photopolymerizable composition contains a pyromethene borate dye as a sensitizing dye.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. An addition-polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter abbreviated as “ethylenic monomer”) contained as a first essential component in the photopolymerizable composition of the present invention. Is a monomer having an ethylenically unsaturated double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system when the photopolymerizable composition is irradiated with actinic rays. In the present invention, the meaning of the monomer is a concept corresponding to a so-called polymer, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer. It is.

Examples of the ethylenic monomer include an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid. Ester, ester obtained by esterification reaction of unsaturated carboxylic acid with polyvalent carboxylic acid and polyvalent hydroxy compound such as aliphatic polyhydroxy compound and aromatic polyhydroxy compound, containing polyisocyanate compound and (meth) acryloyl Examples include an ethylenic compound having a urethane skeleton reacted with a hydroxy compound.

In this specification, "(meth) acryloyl-" and the like mean "acryloyl- or methacryloyl-" and the like. The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not particularly limited. For example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentane Acrylic esters of aliphatic polyhydroxy compounds such as erythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and the like. Methacrylic acid ester in which acrylate was replaced with methacrylate, and similarly itaconate Itaconic acid esters, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

Examples of the ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. And methacrylic acid esters.

The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound does not necessarily have to be a single ester. Representative examples include acrylic acid, phthalic acid and ethylene glycol condensate, acrylic acid, maleic acid and diethylene glycol condensate, methacrylic acid, terephthalic acid and pentaerythritol condensate, acrylic acid, adipic acid, And condensates of butanediol and glycerin.

Examples of the ethylenic monomer having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, and isophorone. Alicyclic diisocyanate such as diisocyanate; tolylene diisocyanate, aromatic diisocyanate such as diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate;
(Meth) acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane and 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane; The reactants are:

Other examples of the polyfunctional ethylenic monomer used in the present invention include epoxy acrylates such as an addition reaction product of a diepoxy compound and hydroxyethyl acrylate; acrylamides such as ethylene bisacrylamide; and phthalic acid. Allyl esters such as diallyl; vinyl group-containing compounds such as divinyl phthalate are useful.

The mixing ratio of these ethylenic monomers is usually 10 to 80% by weight, preferably 20 to 70% by weight of the total solids of the photopolymerizable composition. The addition-polymerizable ethylenic monomer used in the present invention contains a phosphate ester compound containing at least one (meth) acryloyl group. This is particularly useful in terms of the characteristics and the removability of the non-image area.
Although not particularly limited, specific examples include compounds represented by the following general formulas (I) and (II).

[0017]

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(In the general formulas (I) and (II), R and R 'represent a hydrogen atom or a methyl group, 1 represents an integer of 1 to 25, and n represents an integer of 1 to 3.) In the compounds represented by the formulas (I) and (II), 1 is 1 to
A value of 10 is particularly preferred in terms of improving the printing durability and the removability of the non-image area. Of the compounds represented by formulas (I) and (II), specific examples of particularly preferred compounds include methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, methacryloxyethylene glycol phosphate, and the like. Can be

The phosphate compound used in the present invention may be a single compound or a mixture of a plurality of compounds. The content of the phosphate compound is preferably from 1 to 50% by weight based on the total amount of the ethylenic monomers. As the radical activator, which is the second essential component of the present invention, any radical activator that can initiate the polymerization of the ethylenic monomer can be used.
In particular, any of them can be suitably used as long as they have photosensitivity to light rays in the visible region. this house,
Examples of an activator that generates an active radical by interacting with a photoexcited sensitizer, such as
Examples thereof include titanocenes, hexaarylbiimidazoles, halogenated hydrocarbon derivatives, diaryliodonium salts, and organic peroxides. In particular, a photopolymerizable composition in which a titanocene and a compound of the formula (I) are combined is particularly preferable because sensitivity, storage stability, adhesion to a coating film base, and the like are particularly good.

As the titanocenes, various ones can be used. For example, JP-A-59-152396
And various titanocenes which are complexes having titanium as a central metal described in JP-A-61-151197. Specifically, a titanocene compound represented by the following general formula (A) is preferable.

[0021]

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(Wherein, R ^{21 to} R ³⁰ each represent a hydrogen atom, a halogen atom, an alkoxy group or a heterocyclic group having 1 to 20 carbon atoms.) More specifically, di-cyclopentadienyl- Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-
2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,
5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-
2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti
-Bis-2,3,4,5,6-pentafluorophenyl-
1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3
-(Pyr-1-yl) -phenyl-1-yl and the like. These may be used in combination of two or more.

As other radical activators, for example, hexaarylbiimidazoles are also suitably used. Various hexaarylbiimidazoles can be used. For example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) Biimidazole, 2,2'-bis (o
-Bromophenyl) -4,4 ', 5,5'-tetra (p
-Iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chloro Phenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-
Bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) ) -4,4 ', 5,5'-tetra (o, p-
Dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Hexaarylbiimidazoles having a halogen substituent on the benzene ring, such as tetra (o, p-dichlorophenyl) biimidazole, are preferred.

These hexaarylbiimidazoles can be used in combination with another kind of biimidazole, if necessary. Biimidazoles are, for example, Bul
l. Chem. Soc. Japan. 33,565 (1
960) and J.M. Org. Chem. 36 [16] 22
62 (1971). In the present invention, it is important to use a pyrromethene borate dye as the sensitizing dye. As the pyromethene borate dye, those having a structure represented by the following general formula (1) are preferable.

[0025]

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In the formula, R ^{1 to} R ⁶ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aromatic heterocyclic group, or —SO ₃ —R ⁸ A group (R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or an onium ion). R ⁷ is a hydrogen atom,
Represents an alkyl group, an aryl group or an aralkyl group,
X ¹ and X ² each represent a halogen atom, an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group. R ¹ ~
The hydrogen atom of the group represented by R ⁸ may be further substituted. ｝

In R ^{1 to} R ⁸ of the general formula (1), examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkyl group include those having 1 to 1 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclopentyl, n-hexyl, cyclohexyl and 2-ethylhexyl.
0, preferably 1 to 8 carbon atoms, particularly preferably 1 carbon atom
To 6 linear or branched or cyclic alkyl groups. Examples of the aryl group include phenyl, naphthyl and the like.
Bicyclic groups are preferred. The aralkyl group preferably has 1 to 10 carbon atoms in the alkyl portion, and examples include benzyl and phenethyl. As the acyl group, for example, an acyl group having 1 to 3 carbon atoms on the carbon chain side, such as acetyl, propionyl, and butyryl, is preferable. As the alkoxycarbonyl group, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and the like have 1 to 1 carbon atoms.
An alkoxycarbonyl group having 3 alkoxy groups is preferred. Examples of the aromatic heterocyclic group include those containing a nitrogen atom, an oxygen atom and a sulfur atom as hetero atoms such as pyrrolyl, furyl, thienyl, pyridyl and pyrimidyl.
Member rings are preferred. These groups may be further substituted, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a hydroxy group and an alkoxycarbonyl group. When R ⁸ represents an alkali metal atom, lithium, sodium and potassium are preferred, and as the onium ion,
Ammonium ion, substituted ammonium ion, iodonium ion, substituted iodonium ion and the like are preferable.

X¹, X^TwoParticularly preferably as halogen
Is an atom. Also R¹~ R⁶Is a hydrogen atom, carbon number 1
To 8 alkyl groups are preferred.¹, R^Three,
R^Four, R ⁶Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
And R^Two, R^Five, R⁷Is a hydrogen atom or an atom having 1 to 6 carbon atoms.
It is preferably a alkyl group. These alkyl groups are
It may have a branched chain and may be substituted.

The pyrromethene borate dye represented by the general formula (1) is described in, for example, US Pat. H. Boyer et al, Heteroa
Tom Chemistry, Vol. 1,5,389
(1990). Representative examples of the sensitizer comprising a pyrromethene borate dye used in the present invention are shown in Table 1 below, but the sensitizer of the present invention is not limited to the following examples.

[0030]

[Table 1]

These sensitizers are used alone or in combination of two or more. The aliphatic amino acid salt and the condensate thereof, which are the third component of the photopolymerization initiation system, have a function of increasing sensitivity when added to the photopolymerizable composition of the present invention.
Although the mechanism for expressing this function is not clear,
In the photopolymerization process, a radical chain transfer agent, a trapping agent for peroxide radicals generated by addition reaction of oxygen or oxygen with radicals, or in a development process after image exposure,
It is considered that the unexposed portion acts as a solubility accelerator for an alkali developing solution, and as a result, exhibits high sensitivity.

The aliphatic amino acid salt used in the present invention is an acidic amino acid salt having a skeleton in which a carbon atom of a carboxyl group and a nitrogen atom of an amino group are bonded via an alkylene chain having at least one carbon atom in the main chain. A salt formed with a carboxylic acid of a basic or neutral amino acid and a monovalent or polyvalent cation, wherein a hydrogen atom of the aliphatic amino acid salt is substituted with another group, Or, those which are condensed directly or via a linking group are included.

As the anion and cation of the aliphatic amino acid salt, both monovalent and polyvalent can be used. The preferred forms of the anion and the cation are separately described below, but the actual compound is a combination thereof. The type and number of the combination can be arbitrarily selected as long as the total valence becomes zero. The preferred structure of the aliphatic amino acid anion is represented by the following general formula (2).

[0034]

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[0035] (wherein, m represents the number of 1 to 10, R ⁹
To R ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. These groups may be further substituted. When m is 2 or more, a plurality of R ¹¹ and R ¹² may be the same or different. In formula (2), R ⁹ is particularly preferably a phenyl group optionally having a substituent, a naphthyl group optionally having a substituent, or a carbon number optionally having a substituent. This is the case with 1 to 15 alkyl groups. More preferred R ⁹ is represented by the following general formula (3)
It is represented by

[0036]

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(Wherein, R ^{13 to} R ¹⁷ each represent a hydrogen atom,
Alkyl group, aryl group, aromatic heterocyclic group, alkoxy group, acyl group, alkoxycarbonyl group, carboxyl group, cyano group, alkenyl group, acryloyloxy group,
An acryloyl group, an aryloxy group, a halogen atom, a formyl group, an alkylcarbonyloxy group, a nitro group, a sulfo group, an alkylthio group, an alkylsulfonyl group, a phenylsulfonyl group, an amino group, and an amide group. These groups may be further substituted. )

In the general formulas (2) and (3), R ^{9 to} R
Preferred as a substituent in each group which may have a substituent represented by ¹⁷ is an alkyl group, an aryl group, an alkoxycarbonyl group, an alkoxy group, an acyl group, an alkylcarbonyloxy group, an allyl group, Vinyl group, aryloxy group, halogen atom, amino group, amide group, acryloyl group, acryloyloxy group,
These groups can also have substituents.

Particularly preferred R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent or an aryl group having 5 to 15 carbon atoms which may have a substituent. No. As those substituents, a hydroxyl group,
Examples thereof include a carboxyl group, a -COO ^- group, an alkoxycarbonyl group, and an alkylcarbonyloxy group. More preferably, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have the above-mentioned substituent is exemplified.

Particularly preferred examples of R ¹¹ and R ¹² include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a phenyl group. Among them, a hydrogen atom is particularly preferred. Further, the condensate of the compound represented by the general formula (2) is a compound in which a plurality of compounds represented by the general formula (2) are bonded directly or via a bonding group at the positions of R ^{10 to} R ¹⁷ , Usually, a 2- to 5-mer is used. The bonding group is not particularly limited as long as it has two or more valences.

[0041]

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[0042] -S -, - O -, - SO 2 -, - O- (C
H ₂ ) _q —O— (q = 1 to 5), —CO—, —C (CH
₃ ) _2- , -C (CF ₃ ) _2- and the like. As the cation constituting the aliphatic amino acid salt, either monovalent or polyvalent can be used, but a monovalent ion is preferable. As the monovalent cation, an alkali metal ion, or an ammonium ion, a phosphonium ion,
Onium ions such as oxonium ions, sulfonium ions, and iodonium ions are mentioned. As the polyvalent cations, alkaline earth metal ions (divalent), or n of the above-mentioned onium ions via a hydrocarbon group Is an n-valent cation formed by bonding. Next, specific examples of the aliphatic amino acid salt and its condensed derivative used in the present invention are shown in Table 2 below. The aliphatic amino acid salt and its derivative used in the present invention are not limited to these specific examples. is not.

[0043]

[Table 2]

[0044]

[Table 3]

These aliphatic amino acid salts or condensation polymers thereof may be used in combination of two or more. The aliphatic amino acid salt preferably used in the composition of the present invention is a salt comprising an anion represented by the general formula (2) (particularly a compound in which R ⁹ is represented by the general formula (3)) and a monovalent cation. It is.

Further, the photopolymerization initiation system used in the present invention may be 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, if necessary.
By adding a hydrogen-donating compound such as N-phenylglycine or alkyl N, N-dialkylbenzoate, the photopolymerization initiation ability can be further enhanced. Of these, particularly preferred are 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-
Compounds having a mercapto group such as triazole, N,
It is an N-dialkyl benzoic acid alkyl ester.

In the photopolymerizable composition of the present invention, in addition to the above essential components, an organic polymer substance is added as a binder for modifying the composition and improving physical properties after photocuring. Is preferred. The binder may be appropriately selected according to the purpose of improving the compatibility, the film-forming property, the developing property, the adhesive property and the like. Specific examples of the organic polymer binder include, for example, the following compounds.

1) Polyolefin polymer; polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymer; polybutadiene, polyisoprene, etc. 3) Polymer having a conjugated polyene structure; polyacetylene polymer, polyphenylene polymer, etc. 4) Vinyl polymer: poly Vinyl chloride, polystyrene,
Vinyl acetate, polyvinyl alcohol, polyacrylic acid,
Polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc.

5) Polyether; polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether ether ketone, polyacetal, etc. 6) Phenol resin; novolak resin, resole resin, etc. 7) Polyester; polyethylene terephthalate, polyphenol Phthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc.

8) Polyamide; Nylon-6, Nylon 66, water-soluble nylon, polyphenylene amide, etc. 9) Polypeptide; Gelatin, casein, etc. 10) Epoxy resin and its modified products; Novolak epoxy resin, bisphenol epoxy resin, novolak epoxy acrylate And modified resins with acid anhydrides 11) Others: polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole,
Polypyrrole, polyaniline, polysulfide, polysulfone, celluloses, etc.

[0051] Among these resins, it is preferable from the viewpoint of preventing pollution since the photopolymerizable composition can be alkali-developed if it contains a resin having a carboxyl group or a phenolic hydroxyl group in the resin side chain or main chain. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability.

Further, acrylic resin is excellent in developability.
Are preferred, and various monomers can be selected to
Because it is possible to obtain polymers, performance and production control
It is more preferable from the viewpoint. As a specific example, for example,
(T) acrylic acid, (meth) acrylic acid ester,
TA) acrylamide, maleic acid, (meth) acryloni
Tolyl, styrene, vinyl acetate, vinylidene chloride, male
Homo- or copolymers of imides, etc., polyethylene
Oxide, polyvinylpyrrolidone, polyamide,
Polyurethane, polyester, polyether, polyethylene
Terephthalate, acetylcellulose, or polyvinyl chloride
Nilbutyral and the like. As a polymer binder
Is in the molecule in terms of solubility in alkaline developers.
A polymer binder having a ruboxyl group is preferable, and among them,
(Meth) acrylic acid ester and at least one
(T) A copolymer containing acrylic acid as a copolymer component
preferable. (Meth) acrylic acid ester
The group to be formed is not particularly limited.₁~ C ₁₆About
Degrees of aliphatic or aromatic hydrocarbon groups are common. molecule
Preferred acid of polymer binder having carboxyl group in it
The value of the valence is from 10 to 250, and the preferred weight average molecular weight
(Hereinafter abbreviated as Mw) is 5,000 to 1,000,000.

It is desirable that these polymer binders have an unsaturated bond in the side chain, and in particular, the following general formulas (4) to (4).
It preferably has at least one type of unsaturated bond represented by (6).

[0054]

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(Wherein R ³⁰ represents a hydrogen atom or a methyl group. R ^{31 to} R ³⁵ each independently represent a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, Having a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent An optionally substituted aryloxy group, an optionally substituted alkylamino group, an optionally substituted arylamino group, an optionally substituted alkylsulfonyl group, or a substituent An arylsulfonyl group optionally having
Represents an oxygen atom, a sulfur atom, an imino group, or an alkylimino group. )

Such a polymer binder is preferable because the photocurability is enhanced by imparting a double bond to the resin side chain, so that the resolution and adhesion can be further improved. As a synthetic means for introducing an ethylenic double bond, for example,
The methods described in JP-B-50-34443, JP-B-50-34444 and the like can be mentioned. Specific examples include a method in which a compound having a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group in combination with a carboxyl group or a hydroxyl group, an acrylic acid chloride, or the like is used. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting it with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained. In particular, a resin obtained by reacting an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

The main constituents of the photopolymerizable composition of the present invention have been described in detail above. The preferred ratio of these components is 100 parts by weight of the polymerizable ethylenic monomer and the photopolymerization initiator. Of the above, the pyromethene sensitizer is preferably 0.01 to 20 parts by weight, and particularly preferably 0.5 to 1 part by weight.
0 parts by weight, more preferably 0.5 to 8 parts by weight, the aliphatic amino acid salt or a condensate thereof is preferably 0.1 to 80 parts by weight, particularly preferably 0.5 to 60 parts by weight, and more preferably 1 to 60 parts by weight. -30 parts by weight. The radical activator is preferably 0.1 to 80 parts by weight, particularly preferably 0.5 to 60 parts by weight.
Parts by weight, more preferably 1 to 30 parts by weight. The polymer binder is preferably 10 to 400 parts by weight, particularly preferably 20 to 200 parts by weight, and more preferably 50 to 2 parts by weight.
It is in the range of 00 parts by weight.

Further, for example, a preferable amount of the pyrromethene sensitizer is 0.1 to 10 parts by weight based on 10 parts by weight of the radical activator.
Parts by weight, more preferably 0.5 to 8 parts by weight, and the preferred amount of the aliphatic amino acid salt or its condensed derivative is 0.5 to 60 parts by weight, further preferably 1 to 30 parts by weight.

The photopolymerizable composition of the present invention may further contain other substances depending on the purpose in addition to the above-mentioned components. For example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol; coloring agents composed of organic or inorganic dyes and pigments; dioctyl phthalate, didodecyl phthalate, tricresyl Plasticizers such as phosphates, sensitivity property improvers such as tertiary amines and thiols, and other additives such as dye precursors can also be added.

Further, the photopolymerizable composition of the present invention may contain a surfactant as a coating property improving agent. Among them, particularly preferred are fluorine-based surfactants. Preferred amounts of the additives described above are 2 parts by weight or less of the thermal polymerization inhibitor, 20 parts by weight or less of the colorant, 40 parts by weight or less of the plasticizer, and 100 parts by weight of the ethylenic monomer. Body weight is less than 30 parts by weight and surfactant is less than 10 parts by weight.

The photopolymerizable composition described above is diluted with an appropriate solvent, coated on a support and dried to form a photosensitive layer, thereby forming an image forming material. When the image forming material is a photosensitive lithographic printing plate, an aluminum support which has been subjected to anodizing after roughening the surface as a support can be suitably used. Examples of the surface roughening method include generally known brush polishing methods, ball polishing methods, electrolytic etching methods, chemical etching methods, liquid honing methods, sand blasting methods, and the like, and combinations thereof. Examples include a ball polishing method, an electrolytic etching method, a chemical etching method, and a liquid honing method. The surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution as necessary. The aluminum plate thus obtained is usually anodized,
Particularly preferred is a method of treating with an electrolytic solution containing sulfuric acid. The method of anodizing with an electrolytic solution containing sulfuric acid is performed according to a conventionally known method, for example, a method described in JP-A-58-21894. Specifically, for example, sulfuric acid having a sulfuric acid concentration of 5 to 50% by weight, preferably 15 to 30% is used, and the temperature is about 5 to 50 ° C, preferably 15 to 50 ° C.
~ 35 ° C, current density 1 ~ 60A / dm ² for 5 seconds ~
This is performed for about 60 seconds. Further, if necessary, a surface treatment such as treatment with an alkali silicate such as sodium silicate or hot water, or immersion in an aqueous solution containing an aqueous polymer compound such as a resin having a cationic quaternary ammonium group or polyvinylphosphonic acid. It can be performed.

The photosensitive composition can be applied by a known method such as dip coating, coating rod, spinner coating, spray coating, roll coating and the like. Further, an oxygen blocking layer can be provided on the above-mentioned photosensitive layer in order to prevent a polymerization inhibition effect by oxygen. Specific examples thereof include water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, and cellulose. Among them, those containing polyvinyl alcohol having particularly high oxygen gas barrier properties are preferable.

The exposure light source applicable to the composition of the present invention is not particularly limited. Examples thereof include a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, and an argon ion. Laser, Y
AG laser, helium neon laser and the like can be particularly preferably used.

The photopolymerizable composition of the present invention can form an image on a support by performing image exposure with such a light source and developing with an aqueous solution containing a surfactant and an alkali. . The aqueous solution may further contain an organic solvent, a buffer, a dye or a pigment. Suitable alkali agents include inorganic alkalis such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. And organic amine compounds such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine. These can be used alone or in combination. As a surfactant,
For example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates;
Anionic surfactants such as alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts and the like; amphoteric surfactants such as alkyl betaines and amino acids can be used. Also,
As the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like can be contained as necessary.

The photopolymerizable composition of the present invention may be used in addition to a photosensitive lithographic printing plate, such as an etching resist for wiring boards, a copper etching resist for gravure, a dry film, a color filter, and a pigment dispersion resist for plasma displays. The composition can be used for various known applications to which the composition can be applied.

[0066]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. <Synthesis of Binder> Synthesis Example 1 Methyl methacrylate / isobutyl methacrylate / isobutyl acrylate / methacrylic acid = 35/20/1
0/35 mol% (preparation ratio) of a copolymer, Mw = 70,000 (hereinafter abbreviated as “binder 1”), 200 parts by weight, 3,
75 parts by weight of 4-epoxycyclohexylmethyl acrylate, 2.5 parts by weight of p-methoxyphenol, 8 parts by weight of tetrabutylammonium chloride, and 800 parts by weight of propylene glycol monomethyl ether acetate are added to a reaction vessel, and the mixture is heated at 110 ° C. for 24 hours in the air. To stir the ethylenic polymer binder (acid value 60, binder-1
Unsaturated groups reacted in 60% of the entire methacrylic acid component. Hereinafter, it is abbreviated as “binding material-2”. ) A solution was obtained.

Synthesis Example 2 Copolymer of (α-methyl) styrene / acrylic acid (trade name “SCX-690” manufactured by Johnson, acid number 24)
0, Mw = 15,000), 855 parts by weight, 3,4-epoxycyclohexylmethyl acrylate 490 parts by weight, p
1.3 parts by weight of methoxyphenol, 4.3 parts by weight of tetraethylammonium chloride, and 1800 parts by weight of propylene glycol monomethyl ether acetate are added to a reaction vessel, and the mixture is stirred at 120 ° C. for 15 hours in air to react with ethylenic polymer. Material (acid value about 170, unsaturated group reacts to about 50% of the whole acrylic acid component of raw material copolymer).
Hereinafter, it is abbreviated as “binding material-3”. ) A solution was obtained.

<Production of Aluminum Support> The aluminum plate was degreased with 3% sodium hydroxide,
Electroetching was performed in a 5 g / l hydrochloric acid bath at 25 ° C. and a current density of 80 A / dm ² for 11 seconds.
Anodizing was performed at 0 ° C. and 11.5 A / dm ² for 15 seconds, washed with water and dried to obtain an aluminum plate for a lithographic printing plate (hereinafter abbreviated as “support-1”).

Examples 1 to 5 The following photopolymerizable composition coating solution-1 was coated on the support-1.
Was applied and dried using a bar coater to a dry film thickness of 2 g / m ² . Further, a photosensitive lithographic printing plate was prepared by applying and drying an aqueous solution of polyvinyl alcohol using a bar coater to a dry film thickness of 3 g / m ² . The sensitivity of the obtained photosensitive lithographic printing plate was evaluated by the following method. The results are shown in Table 3.

Photopolymerizable Composition Coating Solution-1 Radical Generator A-1 ^{* 1} 5 parts by weight Radical Generator A-2 ^{* 1} 5 parts by weight Sensitizer 1 ^{* 1} 1.4 parts by weight Sensitizer 2 ^{* 1} 0.6 parts by weight Amino acid salts shown in Table 3 (the numbers in the table indicate the added parts by weight) Ethylene monomer-1 ^* 122 parts by weight Ethylene monomer-2 ^* 122 parts by weight Ethylene Functional monomer-3 ^{* 1} 11 parts by weight Polymer binder-2 26 parts by weight Polymer binder-3 10 parts by weight Pigment (P.B. 15: 6) 4 parts by weight Disperbyk 161 (manufactured by Big Chemie) 2 Parts by weight Fluorosurfactant S-381 manufactured by Asahi Glass Co., Ltd. 0.3 parts by weight Propylene glycol monomethyl ether acetate 300 parts by weight Cyclohexanone 645 parts by weight Methyl cellosolve 200 parts by weight * 1;

Evaluation items <Sensitivity> After exposing the photosensitive lithographic printing plate using a diffraction spectral irradiation apparatus (RM-23, manufactured by Narumi), 0.8% by weight of anhydrous sodium carbonate and Perex NBL (Kao Corporation) Developed by immersing in an aqueous solution containing 3% by weight at 25 ° C. for 30 seconds and rubbing with a sponge seven times, and based on the height of the obtained cured image, the light energy required for photocuring with a light beam of 532 nm. The amount was determined.

Comparative Example 1 Instead of sensitizers 1 and 2 used in Example 1,
A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 using a coating solution having the same composition except that sensitizer 3 which was a benzopyran-based dye was used, and the evaluation was performed in the same manner. As a result, the sensitivity was low. . Comparative Example 2 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1, except that N-phenylglycine was used instead of the aliphatic amino acid salt used in Example 1, and a coating solution was prepared. As a result, an odor was generated during coating and drying.

<Measurement of Odor> Each 1 g of the amino acid salt or N-phenylglycine used in each coating solution was applied to a coating solvent 5
0 g, and the solution was heated to 40 ° C. and judged by the odor felt at a distance of 30 cm. When the odor was severe, it was evaluated as x, and when no odor was felt, it was evaluated as ○. From the above results,
Table 3 summarizes and displays them.

[0074]

[Table 4]

[Ethylene monomer] Monomer-1

[0076]

Embedded image

Monomer-2

[0078]

Embedded image

Monomer-3

[0080]

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[Radical generator]

[0082]

Embedded image

[Sensitizer]

[0084]

Embedded image

[0085]

The photopolymerizable composition of the present invention has high sensitivity, good developability, and good solubility of the contained photopolymerization initiator, so that coating defects hardly occur. It is useful when used as a forming material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA01 AA04 AB03 AC01 AD01 BC13 BC31 BC65 BC84 CA27 CA39 CA41 CA48 2H096 AA06 AA26 BA05 EA02 EA04 4J011 QA03 QA04 QA12 QA13 QA15 QA17 QA22 QA42 QA28 QA24 SA88 UA01 UA02 VA01 WA01

Claims (9)

[Claims] 1. An addition polymerizable compound having at least one ethylenically unsaturated double bond, a radical activator,
What is claimed is: 1. A photopolymerizable composition containing a sensitizing dye and an aliphatic amino acid salt, wherein the photopolymerizable composition contains a pyromethene borate dye as a sensitizing dye. 2. The photopolymerizable composition according to claim 1, wherein the pyromethene borate dye is selected from dyes having a structure represented by the following general formula (1). Embedded image Wherein R ^{1 to} R ⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aromatic heterocyclic group, or-
Represents an SO ₃ —R ⁸ group (R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or an onium ion). R ⁷ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and X ¹ and X ² represent a halogen atom, an alkyl group, an aryl group, an aralkyl group and an aromatic heterocyclic group, respectively. These groups may be further substituted. ｝ 3. The photopolymerizable composition according to claim 1, wherein the anion constituting the aliphatic amino acid salt is an anion represented by the following general formula (2) and / or a condensate thereof. Composition. Embedded image (Wherein, m represents an integer of 1 to 10, and R ⁹ , R ¹⁰ , R ¹¹
And R ¹² each represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. These groups may be further substituted. When m is 2 or more, a plurality of R ¹¹ and R ¹²
May be the same or different. ) 4. The photopolymerizable composition according to claim 3, wherein the aliphatic amino acid salt is a salt of an anion represented by the general formula (2) and a monovalent cation. 5. The photopolymerizable composition according to claim 3, wherein, in the general formula (2), R ⁹ has a structure represented by the following general formula (3). Embedded image (Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a hydrogen atom, an alkyl group, an aryl group, an aromatic heterocyclic group,
Alkoxy group, acyl group, alkoxycarbonyl group, carboxyl group, cyano group, alkenyl group, acryloyl group, acryloyloxy group, aryloxy group, halogen atom, formyl group, alkylcarbonyloxy group, nitro group, sulfo group, alkylthio group, Represents an alkylsulfonyl group, an arylsulfonyl group, an amino group or an amide group. These groups may be further substituted. ) 6. The photopolymerizable composition according to claim 1, wherein the cation constituting the aliphatic amino acid salt is a monovalent alkali metal ion or onium ion. 7. The method according to claim 1, wherein the radical activator contains at least one kind of titanocene.
The photopolymerizable composition according to any one of the above. 8. The method according to claim 1, wherein the addition-polymerizable compound has at least one compound.
2. A phosphate compound having two acryloyl groups or methacryloyl groups.
8. The photopolymerizable composition according to any one of items 1 to 7. 9. A photosensitive lithographic printing plate having a photosensitive resin layer on an aluminum substrate which has been subjected to a surface roughening treatment and an anodic oxidation treatment and further subjected to a hydrophilic treatment if necessary. A photosensitive lithographic printing plate formed of the photopolymerizable composition according to any one of claims 1 to 8.