JPH103165A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist composition superior in sensitivity and resolution and suitable for forming a positive image, by incorporating a polymer having specified monomer units and a compound for lowering the solubility of this polymer to an alkaline solution. SOLUTION: This photosensitive composition contains a polymer having monomer units each represented by formula I or II and a compound for lowering the solubility of the polymer to an alkaline solution. In formula I and II, each of X1 and X2 is a divalent bonding group; Y is H atom or a carboxyl group; Z is H atom or an alkyl group or the like; R is H atom or an aliphatic group or the like; and each of (m) and (n) is 0 or 1. The monomer of formula I, can be embodies by N-(4-hydroxy phenyl)acryl- or methacryl-amide, and o- hydroxystyrene and the like, and the monomer of formula II can be embodied by acrylic, methacrylic, and maleic acids, and maleic anhydride, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition having excellent sensitivity and resolution suitable for use in a lithographic printing plate material.

[0002]

2. Description of the Related Art Conventionally, an acid generator is used as a photosensitizer, and a chemical forming a pattern by utilizing a change in solubility in a developing solution in a secondary chemical reaction caused by the catalytic action of an acid generated by exposure. Amplified resist compositions are known and are described, for example, in Synthetic Organic Chemistry, 49 , 437 (1991).
And Textiles and Industry, 47 , 358 (1991). Japanese Patent Application Laid-Open No. 7-128855 discloses that an alkali-soluble resin is made insoluble in alkali by combining an alkali-soluble resin with a specific acid generator. US Pat. No. 4,708,925 discloses an alkali-soluble novolak resin. And a combination of an onium salt are disclosed in JP-A-4-120.
No. 544 describes a combination of an onium salt or an organic halide, a photoacid generator, and a novolak resin having a specific structure. JP-A-6-43633 describes that a positive image is formed by adding a divalent squarium salt having a specific structure.

[0003]

However, in these methods, high sensitivity cannot be obtained, and the SN ratio between an exposed portion and an unexposed portion is not improved.
There is a problem that the ratio is small.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition having excellent sensitivity and resolution and suitable for forming a positive image.

[0005]

The object of the present invention is to provide a polymer having a monomer unit represented by the general formula (1) or (2) (hereinafter also referred to as the polymer of the present invention). And a photosensitive composition containing a compound that reduces the solubility of the polymer in an alkaline solution; a polyurethane resin having a hydrophilic group; a polyester resin having a hydrophilic group; and a polyamide resin having a hydrophilic group. A photosensitive composition containing a species and a compound that reduces the solubility of the resin in an alkaline solution, wherein the photosensitive composition contains an infrared absorbing dye,
The compound that lowers the solubility is a boron salt, a thiopyrylium salt, an aluminate complex or an iron arene complex, or contains a monovalent cationic infrared absorbing dye and a boron salt or an aluminate complex in combination. And a thiopyrylium salt or an iron arene complex.

Hereinafter, the present invention will be described in detail.

In the present invention, at least one resin selected from the polymer of the present invention, a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group is used as a binder. Thereby, the adhesiveness to the support can be improved, and the SN ratio between the exposed portion and the unexposed portion can be increased.

The monomers represented by the general formula (1) include N- (4-hydroxyphenyl) acrylamide,
N- (4-hydroxyphenyl) methacrylamide, o
-Hydroxystyrene, p-hydroxystyrene, m-
Monomers having an aromatic hydroxyl group such as hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacryl Amide, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5
-Hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide,
Examples include monomers having an aliphatic hydroxyl group such as hydroxyethyl vinyl ether.

Examples of the monomer represented by the general formula (2) include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride. .

Next, a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group will be described. In the present invention, as the hydrophilic group, those having a carboxyl group, a hydroxyl group, a sulfonium group, an amino group and a sulfonamide group in a side chain are preferable.

The polyurethane resin having a hydrophilic group of the present invention has at least one kind of the above-mentioned hydrophilic group and has at least one kind selected from urethane bond, urea bond, burette bond and allophanate bond in the main chain. It refers to a polymer containing a repeating unit, and such a bond is formed mainly by selecting a reactive group that undergoes an addition reaction with an isocyanate.

The diisocyanate compound preferably used in this reaction includes conventionally known 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,
Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl-4,4'-diisocyanate; aliphatic diisocyanate compounds such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone Alicyclic diisocyanate compounds such as diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, and 1,3- (isocyanatomethyl) cyclohexane; Reaction products of three or more molecules of these diisocyanate compounds; Isocyanate compound having three or more functional generated by the reaction product of a trivalent or higher polyhydric alcohols can be preferably used.

Examples of the polyfunctional alcohol which forms an urethane bond by an addition reaction with an isocyanate compound include ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octanediol, and the like.
Aliphatic diols such as diethylene glycol and triethylene glycol; glycerin, trimethylolethane,
Aliphatic polyfunctional alcohols such as trimethylolpropane, pentaerythritol, diglycerin, 1,2,6-hexanetriol, sorbitol, mannitol, glucose; polyesters having a hydroxyl group at the end by condensation of dicarboxylic acid and polyhydric alcohol Polyols; ring-opening polymerization of alkylene oxide or polyether polyol added to alkylene oxide and polyhydric alcohol.

According to the alcohol valency of these compounds,
The desired reaction product can be obtained by adding the isocyanate at a ratio of 2 mol per 1 mol of the hydroxyl group and reacting.

In order to impart a hydrophilic group to the polyurethane resin, a method of polymerizing a urethane prepolymer having an isocyanate group at the terminal with a diol having a tertiary amino group and quaternizing the tertiary amino group; A method in which a urethane prepolymer having an isocyanate group remaining therein is polymerized with a diol having a tertiary amino group, and the tertiary amino group is neutralized with an acid to form an amine salt; A method of polymerizing with a diol having a salt; a method of polymerizing a urethane prepolymer having terminal isocyanate groups with diaminophenylcarboxylate and removing the solvent; and a method of forming terminal isocyanate groups of urethane prepolymer having terminal isocyanate groups. Blocking with a compound such as sodium bisulfite; A method of polymerizing a urethane prepolymer leaving a cyanate group with diaminoalkane sulfonate; a method of polymerizing a urethane prepolymer leaving an isocyanate group at a terminal with bis (2-cyanoethylamino) ethane; leaving an isocyanate group at a terminal A method of polymerizing a urethane prepolymer with an alkylene oxide of a long-chain alcohol, and the like. In addition, the method described in “Polyurethane Resin Handbook” edited by Keiji Iwata, Nikkan Kogyo Shimbun, pages 496-502, etc. Can be adopted.

As commercially available polyurethane resins that can be employed in the present invention, Takelac W Series (W-621, W-6015, W-7004, W-704) manufactured by Takeda Pharmaceutical Co., Ltd.
511, W-635, XW-76-P15, XW-74
-P6012C, ACW-31H, ACW-54HD,
XW-904-X05, XW-97-W4 to polyester urethane self-emulsifying type) and (W-310, W-5)
12-polyester urethane forced emulsification type), an alkoxysilyl group-containing series manufactured by Takeda Pharmaceutical Company Limited (XW
-77-X25, XW-75-X09, XW-74-X
13, XS-72-V01, XS-72-V02, XS
-72-V03, XS-72-V04, XS-72-V
05-Polyester urethane self-emulsifying type), High-tack series (S-8531, S
-8532, S-8533, S-8530, S-852
9, S-8528, S-6254, S-6262, B-
1306), NeoRez series (R-960, R-962, R-972, R-974, manufactured by Kusumoto Kasei Co., Ltd.)
R-9314, R-9320, R-9617, XR-9
621, XR-9624, R-9637, XR-967
9, XR-9699, XR-9770 to aliphatic polyester urethane), NeoRez series (R-966, R-967, XR-9000, AX-) manufactured by Kusumoto Chemicals, Inc.
311, AX-7113 to aliphatic polyether urethane), NeoRez series (R-9, manufactured by Kusumoto Kasei Co., Ltd.)
40, R-9030, XR-9409, R-9920,
XR-7061-aromatic polyether urethane), NeoRez series manufactured by Kusumoto Kasei Co., Ltd. (XU-7015,
R-9603-special urethane, aliphatic polycarbonate urethane), iodosol series (9D102, 9D250Z, 9D232) manufactured by Kanebo Uenushi Corporation.
Z), Neotan series manufactured by Toa Gosei Chemical Industry Co., Ltd. (U
E-1101, UE-1200, UE-1300, UE
-1402, UE-2103, UE-2200, UE-
2600, UE-2900 to polyester urethane),
Neotan Series (UE-5) manufactured by Toa Gosei Chemical Industry Co., Ltd.
404, UE-5600 to polyether urethane), Takamatsu Yushi Co., Ltd. Enresin series (R-1489, R
-1780), Crown Bond Series (UA-28, UA-41, U-176R, RI-7) manufactured by Takamatsu Yushi Co., Ltd.
93, RI-623, U-113), Dispacoll series manufactured by Sumitomo Bayer Urethane Co., Ltd. (U-42, U-
53, KA8481 and KA8584).

The polyester resin having a hydrophilic group of the present invention refers to a polymer having at least one kind of the above-described hydrophilic group and containing a repeating unit of an ester bond in a main chain,
A method for synthesizing a resin having such an ester bond is described in, for example, “Polyester Resin Handbook”, by introducing a hydrophilic group into a prepolymer of a polyester resin formed by the method described on pages 21 to 28 by an arbitrary method, do it. Commercially available polyester resins that can be employed in the present invention include Pesresin A series (110,
120,121,193,510,610,810～ hydrophilic group -SO ₃ R), Takamatsu Oil & Fat Co., Ltd. PESRESIN A
Series (210, 620, 820-hydrophilic group is -CO
OR), Takamatsu Yushi Co., Ltd. Pesresin A series (11
5G, 124G, 124GH, 193G, 215G, 5
15G, 615G, 813GL~ hydrophilic group -SO ₃ R
Glycidyl), Takamatsu Oil & Fat Co. PESRESIN A series (124S, 115S～ hydrophilic group and -SO ₃ R Si
(OR) ₃ ), plus coat series (Z-3402, Z-4121, Z-446, Z-
461, Z-448, Z-441, Z-450, Z-7
10, Z-711, Z-770, Z-766 to water-soluble), plus coat series (Z
-802, Z-3109, Z-3308, Z-857,
Z-850, Z-802, Z-856, Z-4201,
RZ-27, RZ-50, RZ-56, RZ-10
5) Toyobo Co., Ltd. Vironal series (MD-
1200, MD-1220, MD-1250, MD-1
100, MD-1330, MD-1930).

The polyamide resin having a hydrophilic group of the present invention refers to a polymer having at least one kind of the above hydrophilic group and having a repeating unit of an amide bond in the main chain, and having such an amide bond. Resin synthesis methods are described in, for example, Tadahiro Miwa, Chemistry of Basic Synthetic Resins <Parent Edition>,
A hydrophilic group may be introduced into the prepolymer of the polyamide resin formed by the method described on the page and polymerized by an arbitrary method. Alternatively, a polyamide resin having a hydrophilic group can be obtained by referring to the method described in “Synthesis and Reaction of Polymer (2)” edited by The Society of Polymer Science, pages 208 to 209. Commercially available polyamide resins that can be employed in the present invention include KW-539 manufactured by Kyogo Chemical Industry Co., Ltd., and KP-2002 and KP-2007 manufactured by Matsumoto Yushi Seiyaku Co., Ltd.

Compounds which reduce the solubility of the polymer of the present invention, the polyurethane resin having a hydrophilic group, the polyester resin having a hydrophilic group and the polyamide resin having a hydrophilic group in an alkaline solution are preferably boron salts and thiopyrylium salts. , An aluminate complex or an iron arene complex.

Examples of the boron salt include compounds having the following structures.

[0021]

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In the formula, R _{1 to} R ₄ each represent an alkyl group (ethyl group, butyl group, etc.), an aryl group (phenyl group, naphthyl group, etc.), an alkynyl group (propenyl group, etc.), a cycloalkyl group (cyclopentyl group, etc.) , A cyclohexyl group, etc.) or a heterocyclic group (thienyl group, pyridyl group, etc.), which may have a substituent. Preferably, at least one of R _{1 to} R ₄ is an aryl group, and at least one other is an alkyl group. The aryl group is preferably a phenyl group or a naphthyl group, and may be substituted with an alkyl group or an alkoxy group. As the alkyl group, one having 1 to 1 carbon atoms
Preferred are alkyl groups of 2, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl. These alkyl groups may be substituted with halogen atoms, alkoxy groups, hydroxyl groups, cyano groups, phenyl groups and the like. X ⁺ represents a counter cation (a Group 5A onium compound such as an alkali metal cation, an ammonium cation, or a phosphonium cation, or a Group 6A onium compound such as a sulfonium or tellurium).

Specific examples of the compounds are described in JP-A-64-1314.
No. 2 and JP-A-2-4804.

Examples of the thiopyrylium salt include compounds having the following structures.

[0025]

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Wherein R _{11 to} R ₁₉ each represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, It represents an aryl group, X ^- represents an anion. Examples of the aluminate complex include compounds having the following structure.

[0027]

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In the formula, at least one of R _{21 to} R ₂₄ is selected from an alkyl group having 3 to 6 carbon atoms, and at least one other is selected from a phenyl group, a benzyl group and an aryloxy group. It is an alkoxy group, and D ⁺ represents a cation.

As the iron-arlene complex, the following (1) to
Compounds having the structure of (3) are mentioned.

[0030]

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[Wherein R ₃₁ is a hydrogen atom, a halogen atom,
It represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X ⁻ represents an anion. ] It is possible to increase the dissolution inhibiting properties of the unexposed portion if the polymer or resin of the present invention and these compounds are used in combination,
In addition, since these salts are decomposed at a lower exposure dose, the SN ratio between the exposed part and the unexposed part can be increased, which is advantageous in sensitivity and resolution. The content of these compounds is 0.5
About 50% by weight, preferably 1 to 30% by weight.

When the photosensitive composition of the present invention is used as a lithographic printing plate material, if the exposure light source is a laser, the effects of the photosensitive composition of the present invention can be fully exhibited and a very high-definition image can be formed. can do. In that case, the photosensitive composition of the present invention preferably contains an infrared absorbing dye to impart sensitivity to laser light. Examples of the infrared absorbing dye that can be employed include a cyanine dye, a squarium dye, and a croconium dye. Dyes, azurenium-based dyes, phthalocyanine-based dyes, naphthalocyanine-based dyes, dithiol metal complex-based dyes, anthraquinone-based dyes, indoaniline metal-complexed dyes, and intermolecular CT dyes are exemplified.

Representative specific examples of the infrared absorbing dye preferably used in the present invention are shown below, but are not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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These dyes can be synthesized by a known method. For example, Nippon Kayaku Kogyo Co., Ltd .:
IR750 (anthraquinone type); IR002, IR0
03 (aluminum type); IR820 (polymethine type); IRG022, IRG033 (diimmonium type); CY-2, CY-4, CY-9, CY-20, manufactured by Mitsui Toatsu Chemicals, Inc .: KIR103, SIR103 (phthalocyanine) KIR101, SIR114 (anthraquinone system); PA1001, PA1005, PA1
006, SIR128 (metal complex), manufactured by Dainippon Ink and Chemicals, Inc .: Fastogen blue 8120, manufactured by Midori Kagaku, Inc .: MIR-101, 1011, 102
A commercially available product such as 1 can also be used. In addition, it is also commercially available from companies such as Nippon Kogaku Dye Co., Ltd., Sumitomo Chemical Co., Ltd., and Fuji Photo Film Co., Ltd.

These dyes may be dissolved in a solvent and added to the photosensitive composition of the present invention. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, amyl acetate, dimethyl phthalate, and benzoate. Esters such as ethyl acid; aromatic hydrocarbons such as toluene, xylene and benzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene and chlorobenzene; diethyl ether, methyl cellosolve, tetrahydrofuran,
Ethers such as dioxane, dimethylformamide, dimethylsulfoxide, bentoxone and the like can be used. The content of the infrared-absorbing dye is not particularly limited as long as it can effectively absorb actinic rays. For example, when exposure is performed with a laser, the reflection density is set to about 0.3 to 1.0. However, it is generally used at 15% by weight or less, preferably at 10% by weight or less.

When the photosensitive composition of the present invention contains an infrared absorbing dye, in the case of a monovalent cationic infrared absorbing dye, a boron salt or an aluminate complex is used in combination with the compound for decreasing the solubility. In the case of a monovalent anionic infrared-absorbing dye, it is desirable to use the compound together with a thiopyrylium salt or an iron arene complex from the viewpoint of reactivity.

Further, the photosensitive composition of the present invention may contain a dye for the purpose of obtaining a visible image by exposure (exposure visible image) and a visible image after development.

As these dyes, those which change color tone by reacting with free radicals or acids can be preferably used. Here, the term "change in color tone" includes any change in color tone from colorless to colored, and change in color tone from colored to colorless or different colored. Preferred dyes are those that form a salt with an acid and change the color tone.

Examples of dyes that change from colored to colorless or different colored tones include, for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) and Oil Blue # 6.
03 [manufactured by Orient Chemical Co., Ltd.], patent pure blue [manufactured by Sumitomo Mikuni Chemical Co., Ltd.], crystal violet, brilliant green, ethyl violet, methyl violet, methyl green, erythrosin B, basic fuchsin, malachite green, oil red, m-
Cresol purple, Rhodamine B, Auramine, 4-
triphenylmethane, diphenylmethane, represented by p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like;
Oxazine, xanthene, iminonaphthoquinone,
Azomethine-based or anthraquinone-based dyes are exemplified.

On the other hand, examples of dyes that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline,
1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p′-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′, p ″ -tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-
Methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p,
Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified.

The dye to be added to the photosensitive composition may be a dye which merely colors the photosensitive composition. As the pigment used for such purposes, organic pigments, for example,
Phthalocyanine pigments, copper phthalocyanine lake blue pigments, dioxazine pigments, sullen pigments, and basic dye lake pigments can be mentioned, and phthalocyanine pigments and dioxazine pigments are preferred. When using these pigments, in order to uniformly disperse in the system, a dispersant,
For example, epsilon caprolactone, cationic surfactant, anionic surfactant, nonionic surfactant,
It is preferable to use in combination with a polyurethane resin, a vinyl resin, an unsaturated polyester or the like (latest, pigment dispersion technology (described by Technical Information Association)).

Of these dyes and pigments, triphenylmethane, diphenylmethane and phthalocyanine are preferred.

The above dye is contained usually in an amount of 0.5 to 10% by weight in the total solid content of the photosensitive composition, preferably in an amount of about 1 to 10% by weight.
The content is 7.5% by weight.

The photosensitive composition of the present invention may contain a sensitizer, wherein the compound having at least one carboxyl group, at least one hydroxyl group and at least one alkyl group having 3 or more carbon atoms is preferable. Examples thereof include condensation type resins of a compound having a carboxyl group, a hydroxyl group or an alkyl group having 3 or more carbon atoms on a benzene ring and an aldehyde or a ketone.
A carboxyl group, a hydroxyl group and an alkyl group having 3 or more carbon atoms may be directly bonded to the trunk of the condensed fat or oil, or may be via a joint. Examples of the compound having one or more carboxyl groups used in the production of the condensation type resin include p-hydroxybenzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, isopropylbenzoic acid, tert- Butylbenzoic acid, 4-hexylbenzoic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 6
-Propyl salicylic acid, 6-lauryl salicylic acid, 6-
Stearyl salicylic acid, 4,6-dimethylsalicylic acid,
p-hydroxy-6-benzoic acid, p-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxy -6-methylbenzoic acid, 2,6-dihydroxybenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dihydroxybenzoic acid , Gallic acid, phloroglucin carboxylic acid,
2,4,5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-
(P-toluyl) gallic acid, protocatechuyl-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl) acetic acid, (2,6-dihydroxyphenyl) acetic acid, (3,4,5- Trihydroxyphenyl)
Acetic acid and the like, among which p-hydroxybenzoic acid, tert-butylbenzoic acid, 6-lauryl salicylic acid and 6-stearyl salicylic acid are particularly preferable.

Examples of compounds used as the condensation unit containing one or more hydroxyl groups include phenol, m-cresol, o-cresol, p-cresol, 3,5-xylenol, carvacrol, thymol, catechol, Resorcin, hydroquinone, pyrogallol, phloroglucin, p-ethylphenol, isopropylphenol, tert-butylphenol, te
rt-butylphenol, tert-octylphenol, isocresol, tert-butylcresol, t
ert-amyl resole, hexyl resole, te
rt-octylcresol, cyclohexyl resole, 2-methylresorcin, 5-methylresorcinol,
-Ethylresorcin, 5-ethylresorcin, 2-propylresorcin, 2-isopropylresorcin, 2-t
tert-butyl resorcinol, 5-butyl resorcinol, 5
-Tert-butyl resorcin, 2-pentyl resorcin, 2-hexyl resorcin, 2-octyl resorcin, 5-chlororesorcin, 5-methoxyresorcin,
2-methyl-5-chlororesorcin, 2-ethyl-5
Chlororesorcin, 2,5-dimethylresorcinol, 2-
Methyl-5-ethylresorcinol, 2-methyl-5-methoxyresorcinol, 2,5-diethylresorcinol, 2-t
tert-butyl-5-methylresorcin, 5-chloropyrogallol, 5-methoxypyrogallol, 5-methylpyrogallol, 5-ethylpyrogallol and 5-tert
-Butylpyrogallol and the like, among which 3,5-xylenol and tert-butylphenol are preferred.

Examples of compounds containing at least one alkyl group in the molecule include tert-butylbenzene, n
-Hexylbenzene, n-dodecylbenzene and the like.

The compound having a carboxyl group, a hydroxyl group and / or an alkyl group having 3 or more carbon atoms and an aldehyde or a ketone used for the condensation of the above condensation type resin can be freely combined with each other. It is also possible to co-condense together. In this case, the charging ratio of the condensation unit of the compound having a carboxyl group, a hydroxyl group and an alkyl group having 4 or more carbon atoms with an aldehyde or a ketone is suitably at least 10 mol% of the entire composition.
It is preferably at least 30 mol%.

The aldehydes and ketones include acetaldehyde, formaldehyde, acetone, methyl ethyl ketone, diethyl ketone, benzaldehyde,
Methylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, acetophenone, 4-methylacetophenone, benzophenone,
Examples thereof include 4-methylbenzophenone and 4,4'-dimethylbenzophenone. Of these, acetaldehyde, acetone and benzaldehyde are particularly preferred.

Examples of the condensation type resin containing a condensation unit of a compound containing a carboxyl group, a hydroxyl group and an alkyl group having at least carbon atoms with an aldehyde or a ketone include hydroxybenzoic acid-xylenol-formaldehyde resin and butyl Benzoic acid-xylenol-formaldehyde resin, lauryl salicylic acid-xylenol-formaldehyde resin, stearin salicylic acid-xylenol-formaldehyde resin, hydroxybenzoic acid-butylphenol-formaldehyde resin, butylbenzoic acid-butylphenol-formaldehyde resin, lauryl salicylate-butylphenol-formaldehyde resin, Stearic acid-butylphenol-formaldehyde resin, propylsalicylic acid-phenol-formaldehyde resin , Dihydroxybenzoic acid - butyl aldehyde resins, these preferably, hydroxybenzoic acid - butylphenol - formaldehyde resins, lauryl salicylic acid - butylphenol - formaldehyde resins, butyl benzoate - butylphenol - formaldehyde resins.

The sensitizer may be a condensate with o-naphthoquinonediazidosulfonic acid.

The photosensitive composition of the present invention may contain a surfactant. In this case, a nonionic surfactant, an anionic surfactant or a fluorine-containing surfactant is preferred.

Examples of the anionic surfactant include higher alcohol sulfates having 8 to 22 carbon atoms, such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, and secondary sodium alkyl sulfate. For example, aliphatic alcohol sulfates such as acetyl alcohol sulfates, for example, sodium salt of acetyl alcohol sulfate, for example, sodium salt of dodisylbenzenesulfonic acid, sodium salt of isopropylnaphthalenesulfonic acid, sodium salt of metanitrobenzenesulfonic acid Alkylarylsulfonates such as C ₁₂ H ₃₃ CO
Examples include sulfonates of alkylamides such as N (CH ₃ ) CH ₂ CH ₂ SO ₃ Na, and sulfonates of dibasic fatty acid esters such as dihexyl sodium sulfonate succinate. Preferred are alkyl sulfonates, alkyl aryl sulfonates, higher alcohol sulfates, alkylamide sulfonates, aliphatic alcohol sulfates, and the like. It is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight.

Although various compounds can be used as the nonionic surfactant, they can be broadly classified into polyethylene glycol compounds and polyhydric alcohol compounds, and the polyethylene glycol compound is more preferably used. Among them, an oxyethylene unit has a repeating structure of 3 or more, and an HLB value (Hydrophi
Non-ionic surfactants having a le-Lipophile Balance of 5 or more, more preferably 10 to 20, are suitable. Specific examples include polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, poperioxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxy Propylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, polyoxyethylene oleamide , Polyoxyethylene castor oil, polyoxyethylene ethylene abiethyl ether, Oxyethylene nonine ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monostearate, polyoxyethylene propylene glycol monostearate, oxyethylene oxypropylene block polymer , Distyrenated phenol polyethylene oxide adduct, tribenzyl phenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate and the like. . The addition amount of these nonionic surfactants is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight. The weight average molecular weight of these nonionic surfactants is 300 to 500.
00 is preferable, and particularly preferably, it is in the range of 500 to 5000. These nonionic surfactants may be used alone or in combination of two or more.

Examples of the fluorinated surfactant which can be used are as follows.

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Commercially available fluorinated surfactants can also be used, for example, Surflon “S-381” and “S-38”.
2 "," SC-101 "," SC-102 "," SC-102 "
103 ”and“ SC-104 ”(both by Asahi Glass Co., Ltd.)
Co., Ltd.), Florard “FC-430”, “FC-43”
1 "," FC-173 "(all from Fluorochemicals-manufactured by Sumitomo 3M), F-top" EF352 "," EF
301 ”and“ EF303 ”(both from Shin-Akita Chemical Co., Ltd.)
Manufactured), Shubego Fuller “8035”, “8036”
(All manufactured by Schwegman), "BM1000",
"BM1100" (all manufactured by BM Himmy),
And MegaFac "F-171" and "F-177" (both manufactured by Dainippon Ink and Chemicals, Inc.).

The fluorine content of the fluorine-containing surfactant is as follows:
It is about 0.05 to 2%, preferably 0.1 to 1%.
The above-mentioned various fluorine-based surfactants can be used alone or in combination.

When the photosensitive composition of the present invention is applied as a photosensitive layer of a lithographic printing plate material, an aluminum support is preferably used. The aluminum plate used for the support includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, and iron is used.

The aluminum plate is preferably subjected to a degreasing treatment to remove rolling oil on the surface prior to electrolytic surface roughening. Examples of the degreasing treatment include a degreasing treatment using a solvent such as trichlene or thinner, and an emulsion degreasing treatment using an emulsion such as kesilon or triethanol. Also, by immersing in an alkaline solution such as caustic soda having a concentration of 1 to 15% at 20 to 90 ° C. for 5 to 10 seconds, it is possible to remove stains and oxide films that cannot be removed only by the above degreasing treatment.

When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support. In this case, an acid such as phosphoric acid, nitric acid, sulfuric acid or chromic acid having a concentration of 10 to 20% is used. Or 10-50 in their mixed acid
It is preferable to immerse at 5 ° C. for 5 seconds to 5 minutes to perform desmut treatment.

The graining method includes a so-called mechanical roughening method for mechanically roughening the surface, a so-called chemical roughening method for chemically dissolving and roughening the surface, and a so-called electrochemical roughening method. There is a so-called electrochemical surface roughening method for roughening the surface. The mechanical surface roughening method includes a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, and the like. The electrochemical surface roughening method includes an electrolytic treatment in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. There is a method to do.

Since a smut is formed on the surface of the support subjected to the graining treatment, it is generally preferable to appropriately perform a treatment such as washing with water or alkali etching to remove the smut. Such a treatment is described in JP-B-48-2
No. 8123, etc.
A treatment method such as a sulfuric acid desmut method described in 3-12739 and the like.

Next, in order to improve abrasion resistance, chemical resistance and water retention, an oxide film is formed on the support by anodizing treatment. In the anodizing treatment, generally, a method of performing electrolysis at a current density of 1 to 10 A / dm ² using an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution is preferably used. US Patent No. 1,41
U.S. Pat. No. 2,768, a method of electrolysis at high current density in sulfuric acid, and a method of electrolysis using phosphoric acid described in U.S. Pat. No. 3,511,661. Can be.

The support subjected to the anodizing treatment may be subjected to a sealing treatment as required. Sealing treatment includes boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment,
It can be performed using a known method such as nitrite treatment.

The support may be further provided with a hydrophilic undercoat layer. As the hydrophilic undercoat layer, U.S. Pat.
No. 461, an alkali metal silicate described in U.S. Pat. No. 1,860,426, a hydrophilic cellulose described in JP-A-60-149491, and JP-A-63-1.
No. 65183, amino acids and salts thereof, hydroxyl-containing amines and salts thereof described in JP-A-60-232998, phosphates described in JP-A-62-19494, and salts described in JP-A-59-19294. For example, a polymer compound containing a monomer unit having a sulfo group described in JP 101651 A can be used. A lithographic printing plate material can be obtained by applying a coating solution obtained by dissolving the photosensitive composition of the present invention in a solvent on the aluminum plate and providing a layer of the photosensitive composition.

Solvents that can be used when dissolving the photosensitive composition include, for example, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol methyl ethyl ether, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethyl sulfoxide,
Examples thereof include dioxane, acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol, acetylacetone, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

As a coating method used for coating the photosensitive composition on the surface of the support, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, Methods such as electrostatic air spray coating, roll coating, blade coating, and curtain coating are used. At this time, the amount of application varies depending on the application, but, for example, 0.05 to 5.0 g as a solid content.
/ M ² is preferred.

The developer used in the development of a lithographic printing plate material using the photosensitive composition of the present invention may be any known developer, but contains an alkali agent and water as essential components. It is preferable to use a liquid. If necessary, carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl replate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone And the like: ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-
Alcohols such as amyl alcohol and methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; organic solvents such as halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzene may be used in combination.

Examples of the alkaline agent contained in the developer include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium or ammonium salts of secondary or tertiary phosphoric acid, and metasilicate. Sodium, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine,
Diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneamine, ethylenediamine, and the like, preferably potassium silicate, sodium silicate, Sodium diphosphate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, monoethanolamine, diethanolamine, and triethanolamine. The alkali agents may be used alone or as a mixture of two or more.

The content of these alkali agents in the developer is usually 0.05 to 8% by weight, preferably 0.5 to 6% by weight.
% By weight.

Further, in order to further improve the storage stability, printing durability and the like, it is preferable to include a water-soluble sulfite in the developer. As such a water-soluble sulfite, an alkali or alkaline earth metal salt of sulfite is preferable, for example, sodium sulfite, potassium sulfite, lithium sulfite,
Magnesium sulfite and the like. The content of these sulfites in the developer composition is usually 0.05 to 4% by weight, preferably 0.1 to 1% by weight.

Further, a solubilizing agent may be included to assist the dissolution of the organic solvent in water. As such a solubilizing agent, it is preferable to use low molecular weight alcohols and ketones which are more water-soluble than the specific organic solvent used. In addition, anionic surfactants, amphoteric surfactants and the like can also be used. Examples of such alcohols and ketones include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxymethylbutanol, N-methylpyrrolidone and the like. It is preferable to use As the surfactant, for example, sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, N-methyl-N
-Sodium pentadecylaminoacetate, sodium lauryl sulfate and the like are preferred. These alcohols,
The amount of the solubilizing agent such as ketones is not particularly limited, but is generally preferably about 30% by weight or less based on the whole developer.

When the photosensitive lithographic printing plate material is exposed to an image and then brought into contact with the above-mentioned developing solution or further rubbed, at 10 to 40 ° C. for 10 to 60 seconds,
The photosensitive composition in the non-image area is completely removed without adversely affecting the exposed area of the photosensitive layer.

[0082]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Support >> An aluminum plate having a thickness of 0.24 mm (material: 1050, tempered H16) was kept at 65 ° C. by 5%
It was immersed in an aqueous sodium hydroxide solution, degreased for 1 minute, and then washed with water. This degreased aluminum plate is
It was immersed in a 10% hydrochloric acid aqueous solution kept at 0 ° C. for 1 minute to neutralize, and then washed with water. Next, the aluminum plate was placed in a 0.3% by weight aqueous nitric acid solution at a temperature of 25 ° C. and a current density of
After roughening the electric field with an alternating current for 60 seconds under the condition of 0 A / dm ² , a desmut treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution kept at 60 ° C. The desmutted roughened aluminum plate was placed in a 15% sulfuric acid solution at a temperature of 25 ° C., a current density of 10 A / dm ² and a voltage of 1
Anodizing treatment was performed for 1 minute under the condition of 5 V, sealing treatment was performed at a temperature of 90 ° C., and hydrophilization treatment was further performed with 3% carboxymethylcellulose salt to prepare a support.

<< Preparation of Photosensitive Lithographic Printing Plate Material >> The following photosensitive composition was applied to the prepared grain support using a wire bar so as to have a dry film thickness of 2.0 μm.
Heat treatment was performed at 0 ° C. for 2 minutes to form a photosensitive layer.

(Photosensitive Composition 1) Methyl methacrylate (MMA) / acrylonitrile (AN) / butyl acrylate (BA) / methacrylic acid (MAA) / hydroxyphenyl methacrylamide (HyPMA) = 40/20/15 / 5/20 of the polymer [wt average molecular weight = 50,000] 89 parts by weight of diphenyl iodonium · PF ₆ ^- 8 parts by weight cyanine dye [manufactured by Nippon Kayaku Co., Ltd.; CY-9] 3 parts by weight of methyl ethyl ketone (MEK) / Propylene glycol monomethyl ether (PGM) = 1/1 in a mixed solvent so that the solid content was 8%.

(Photosensitive Composition 2) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 80 parts by weight Diphenyliodonium PF ₆ ⁻ 8 parts by weight Cyanine dye [CY-9] manufactured by Nippon Kayaku Co., Ltd. 3 parts by weight tert-butylbenzoic acid-tert-butylphenol-formaldehyde resin [weight-average molecular weight = 2000] 8 parts by weight fluorinated surfactant [large Nippon Ink Co., Ltd .; F-177] 1 part by weight It was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 3) High molecular polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 81 parts by weight diphenyliodonium PF ₆ ⁻ 8 parts by weight Cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] 3 parts by weight tert-butylbenzoic acid-tert-butylphenol-formaldehyde resin [weight average molecular weight = 2000] 5 parts by weight fluorinated surfactant [large Nippon Ink Co., Ltd .; F-177] 1 part by weight 1,3,5-tetraacetoxymethylbenzene 2 parts by weight It was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 4) A polymer having MMA / AN / BA / MAA / 4-hydroxybutyl acrylate (4-HBA) = 40/20/15/5/20 [weight average molecular weight = 5000] a solid content of 8% CY-9] 2 parts by weight MEK / PGM = 1/1 mixed solvent; 6 parts by weight cyanine dye [manufactured by Nippon Kayaku Co., Ltd. ^- 0] 80 parts by weight of diphenyl iodonium · PF ₆ Dissolved in the same manner.

[0089] (Photosensitive composition 5) MMA / AN / BA / MAA = 60/20/15/5 of the polymer [wt average molecular weight = 50,000] 80 parts by weight of diphenyl iodonium · PF ₆ ^- 6 parts by weight 2 parts by weight of a cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] dissolved in a mixed solvent of MEK / PGM = 1/1 to a solid content of 8%.

[0090] (Photosensitive composition 6) hydroxystyrene / BA / MMA // MAA = 70 /10 / height min son polymer 5/15 [weight-average molecular weight = 50,000] 80 parts by weight of diphenyl iodonium · PF ₆ ^- 6 Part by weight Cyanine dye [CY-9] (manufactured by Nippon Kayaku Co., Ltd.) 2 parts by weight The solid was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 7) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 80 parts by weight Diphenyliodonium PF ₆ ⁻ 6 parts by weight Polymethine dye [manufactured by Nippon Kayaku Co., Ltd .; IR-820B] 2 parts by weight The solid was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 8) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 80 parts by weight diphenyliodonium PF ₆ ⁻ 6 parts by weight Nickel complex dye [NKX-113, manufactured by Nippon Kayaku Co., Ltd.] 2 parts by weight It was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 9) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 80 parts by weight diphenyliodonium PF ₆ ⁻ 6 parts by weight Cyanine dye [manufactured by Konica Corporation; F-1070] 2 parts by weight The solid was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 10) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 80 parts by weight diphenyliodonium PF ₆ ⁻ 6 parts by weight Phthalocyanine dye (manufactured by Konica Corporation; TX-208A) 2 parts by weight The solid was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Photosensitive Composition 11) 80 parts by weight of a high molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000]

[0096]

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3 parts by weight of cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] 3 parts by weight MEK / PGM = 1/1 was dissolved in a mixed solvent so that the solid content became 8%.

(Photosensitive Composition 12) 80 parts by weight of a high molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000]

[0099]

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3 parts by weight of cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] 3 parts by weight MEK / PGM = 1/1 was dissolved in a mixed solvent so that the solid content became 8%.

[0102] (Photosensitive composition 13) urethane emulsion [Takeda Chemical Industries Co., Ltd .; Takelac XW-76-P1 5] 89 parts by weight of diphenyl iodonium · PF ₆ ^- 8 parts by weight Cyanine dye [manufactured by Nippon Kayaku Co., CY-9] 3 parts by weight Dissolved in a mixed solvent of water / acetone = 8/2 so that the solid content became 8%.

[0102] (Photosensitive composition 14) Polyester emulsion [manufactured by Takamatsu oil Corporation; PESRESIN A-513d] 89 parts by weight of diphenyl iodonium · PF ₆ ^- 8 parts by weight Cyanine dye [manufactured by Nippon Kayaku Co., CY- 9] 3 parts by weight It was dissolved in a mixed solvent of water / acetone = 8/2 so that the solid content became 8%.

[0103] (Photosensitive composition 15) Polyamide emulsion [Matsumoto Yushi-Seiyaku Co., Ltd., KP-2002] 89 parts by weight of diphenyl iodonium · PF ₆ ^- 8 parts by weight Cyanine dye [manufactured by Nippon Kayaku Co., Ltd.; CY- 9] 3 parts by weight It was dissolved in a mixed solvent of water / acetone = 8/2 so that the solid content became 8%.

(Photosensitive Composition 16) 89 parts by weight of urethane emulsion [Takerac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.]

[0105]

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3 parts by weight of cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] 3 parts by weight The solid was dissolved in a mixed solvent of water / acetone = 8/2 so that the solid content became 8%.

(Photosensitive Composition 17) 89 parts by weight of urethane emulsion [Takelac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.]

[0108]

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3 parts by weight of phthalocyanine dye (manufactured by Konica Corporation; TX-208A) 3 parts by weight It was dissolved in a mixed solvent of water / acetone = 8/2 so that the solid content became 8%.

(Comparative Photosensitive Composition 1) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 89 parts by weight 2,4,6 -Tris (trichloromethyl) -S-triazine 8 parts by weight Cyanine dye [manufactured by Nippon Kayaku Co., Ltd .; CY-9] 3 parts by weight The solid content becomes 8% in a mixed solvent of MEK / PGM = 1/1. Was dissolved.

[0111] (Comparative light-sensitive composition 2) m-cresol / p- cresol = 6/4 acetone condensate [weight average molecular weight = 50,000] 89 parts by weight of diphenyl iodonium · PF ₆ ^- 8 parts by weight Cyanine dye [Japan of CY-9] manufactured by Yakuhin Co., Ltd. 3 parts by weight The solid was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

(Comparative Photosensitive Composition 3) High molecular weight polymer of MMA / AN / BA / MAA / HyPMA = 40/20/15/5/20 [weight average molecular weight = 50000] 89 parts by weight diphenyliodonium PF ₆ ^- 8 parts by weight

[0113]

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It was dissolved in a mixed solvent of MEK / PGM = 1/1 so that the solid content became 8%.

<< Image formation and evaluation >> (Evaluation of development S / N ratio) The obtained photosensitive lithographic printing plate material was subjected to scanning exposure from the photosensitive layer side while focusing on the photosensitive layer under the following conditions under the following conditions. Exposure.

Light source: Semiconductor laser LT0 manufactured by Sharp Corporation
90MD, output: 100 mW, main wavelength: 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch: 6 μm 30 using a diluent of developer SDR-1 manufactured by Konica Corporation.
The photosensitive layer in the exposed area was eluted by immersion at 30 ° C. for 30 seconds, washed with water and dried to form an image. By changing the dilution ratio, the range of the dilution ratio (stock solution / water) in which there was no film burrs and the non-image area was not stained was evaluated. However, for photosensitive composition 3, 1
After passing between a pair of heat rolls heated to 00 ° C., it was immersed in a developer.

(Evaluation of sensitivity) 0.5 m at a beam diameter of 4 μm
Solid scanning exposure was performed so that an image of mx 0.5 mm was formed, and the average exposure E on the material surface when an image was formed was evaluated on the following five levels. The development was performed at the center dilution ratio in the range obtained in the evaluation of the development S / N ratio.

5 ... E≤100 4 ... 100 <E≤250 3 ... 250 <E≤400 2 ... 400 <E≤600 1 ... 600 <E (Evaluation of resolution) Scanning exposure was performed with a beam diameter of 4 μm and a scanning pitch of 4 μm. The number N of resolvable lines per mm when an image was formed at the average exposure amount on the surface of the image forming material was evaluated on the following four scales.

4 ... 125≤N 3 ... 120≤N <125 2 ... 110≤N <120 1 ... N <110 (Evaluation of Adhesiveness) Regarding the photosensitive compositions 13 to 17 and the comparative photosensitive composition 2, The adhesiveness was evaluated as follows.

A lithographic printing plate is prepared by exposing and developing such that a 50% halftone dot portion of the formed image is reproduced with a dot area ratio of 55%. Net pattern part manufactured by Nichiban Co., Ltd .; peel angle 180 °, 30 m using cellophane tape
An m / sec peeling test is performed, and observation is performed with a 200-power loupe to confirm that there is no missing net pattern. Further, manufactured by Dainichi Seika Co., Ltd .; Ultra Plate Cleane
Each was immersed in r (acid) for 30 minutes, a peeling test was performed in the same manner, a net pattern was observed with a loupe, and evaluated according to the following criteria.

◎: No change at all.…: Slight removal of dye and change in density. Are shown in Table 1.

[0122]

[Table 1]

[0123]

According to the present invention, a photosensitive composition excellent in sensitivity and resolution can be obtained, and the composition is suitable for a lithographic printing plate material because it is excellent in developability and image adhesion. .

──────────────────────────────────────────────────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 7/039 7/039 (72) Inventor Tatsuichi Maebashi Hino, Tokyo Konica Stock Exchange, Sakura-cho, Ichigo

Claims (5)

[Claims] 1. A photosensitive composition comprising: a polymer having a monomer unit represented by the following general formula (1) or (2); and a compound that reduces the solubility of the polymer in an alkaline solution. Composition. Embedded image Wherein X ₁ and X ₂ are divalent linking groups, Y is hydrogen or carboxyl group, Z is hydrogen, alkyl group or carboxyl group, R is hydrogen, aliphatic group or aromatic group, m And n
Represents 0 or 1. ] 2. It contains at least one selected from a polyurethane resin having a hydrophilic group, a polyester resin having a hydrophilic group, and a polyamide resin having a hydrophilic group, and a compound that reduces the solubility of the resin in an alkaline solution. A photosensitive composition comprising: 3. The photosensitive composition according to claim 1, further comprising an infrared absorbing dye. 4. The photosensitive composition according to claim 1, wherein the compound that reduces the solubility is a boron salt, a thiopyrylium salt, an aluminate complex or an iron arene complex. 5. A monovalent cationic infrared absorbing dye and a boron salt or an aluminate complex, or a monovalent anionic infrared absorbing dye and a thiopyrylium salt or an iron arene complex. 5. The method according to claim 4, wherein
4. The photosensitive composition according to item 1.