JPH10153863A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition capable of forming an image high in sensitivity and good in resolution with a low exposure energy by using a combination of a specified complex or salt and a specified binder resin having a hydrophilic group. SOLUTION: This photosensitive composition contains a kind of iron allene complex represented by formula I, a pyrylium salt represented by formula II, and an aluminate complex salt represented by formula III, and in formulae I-III, each of R1 -R9 is an H atom or an alkyl, alkenyl, alkoxy, or aryl group; X<-> is an anion; and D<+> is a cation. As the boron salt, it is not especially limited but a compound comprising an anion moiety containing a boron atom and a cation moiety. The binder resin can be embodied by an acrylic resin having a hydrophilic group, phenol resins, polyester resins, and polyurethane resins. The lithographic printing plate made by using this positive photosensitive composition can form an image high in sensitivity and good in resolution due to improvement of developability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition capable of forming a high-resolution image with high sensitivity to light rays in the visible to near infrared region.

[0002]

2. Description of the Related Art Conventionally, a photoacid generator has been used as a photosensitive agent, and a secondary chemical reaction is caused by the catalytic action of an acid generated by exposure to cause a change in a dissolution rate in a developing solution to form a pattern. A chemically amplified photosensitive composition is known. For example, a photosensitive composition using an onium salt as a photoacid generator and a novolak resin as a binder is disclosed in US Pat. No. 4,708,925. . In this technique, a composition comprising a novolak resin and an onium salt is formed by adding an onium salt to a novolak resin, the solubility of the novolak resin in a developer originally possessed by the composition is reduced, and the composition is irradiated by light. By decomposing, the solubility of the novolak resin in the developing solution is increased, and a positive image is formed by utilizing the difference in solubility in the developing solution between the exposed portion and the unexposed portion of the photosensitive layer.

Further, a chemically amplified resist composition using a squarylium dye together with a binder and a photoacid generator is disclosed in JP-A-6-43633. This uses a squarylium dye as a sensitizer (extends the photosensitive wavelength to longer wavelengths) of the photoacid generator to enhance the function of the photoacid generator and produce a compound of a binder and a photoacid generator. Then, the compound is decomposed by exposure to light, and it is presumed that the difference in solubility between the exposed portion and the unexposed portion of the photosensitive layer in a developing solution is used, and as a result, a positive or negative image is obtained.

However, since these techniques have low sensitivity, the difference in solubility between the exposed part and the unexposed part with respect to the developing solution is small, and the decomposition performance is such that the exposed part is completely dissolved and removed with the developing solution with a small exposure energy. It was low and had a problem in terms of developability.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to form a high-resolution image with high sensitivity even at a lower exposure energy and improvement in developability. To provide a positive photosensitive composition that can be used.

[0006]

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

(1) A positive photosensitive composition comprising at least one selected from the following group A and at least one selected from group B:

[Group A] a) At least one iron arene complex represented by the following formulas (1) to (3):

[0009]

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R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and X ⁻ represents an anion.

B) a pyrylium salt represented by the following structure:

[0012]

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[0013] R ₁ to R ₉ is 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, an aryl group having 6 to 12 carbon atoms, X ^- Represents an anion.

C) a boron salt; d) an aluminate complex represented by the following structure:

[0015]

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At least one of R _{1 to} R ₄ has 3 to 6 carbon atoms.
And at least one is selected from a phenyl group, a benzyl group and an aryloxy group, and the other is selected from an alkyl group, an alkenyl group and an alkoxy group. D ⁺ is a cation.

[Group B] Acrylic resins containing a hydrophilic group in the molecule, and phenolic, polyester and polyurethane resins.

That is, the present inventors can increase the dissolution inhibiting property of the unexposed area by using the above specific complex or salt in combination with a specific binder having a hydrophilic group, The amount of the binder and the complex or the complex of the salt can be decomposed in an amount, so that the difference in solubility between the exposed part and the unexposed part can be increased, and an image with higher sensitivity and good resolution can be formed. The inventors have found that a positive photosensitive composition can be obtained, and have reached the present invention.

Hereinafter, the present invention will be described in detail.

Description of [Group A] The positive photosensitive composition of the present invention is characterized by having at least one selected from Group A. Group A includes iron arene complexes, pyrylium salts, boron salt compounds, and aluminate complexes.

The iron arene complex is represented by the following formula (1)
And (3) iron arene complexes.

[0022]

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[0023] Incidentally, R ₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and X ^- is an anion Represent. Examples of the halogen atom include bromine, chlorine and iodine, and examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl. Examples of the alkenyl group having 1 to 6 carbon atoms include propylenyl, isopropylenyl, 1-butenyl, 2-butenyl, isobutylenyl, pentenyl, hexenyl and the like. Examples of the aryl group having 6 to 12 carbon atoms include benzene and naphthalene. , benzothiazole, benzoxazole, Bentaren, benzimidazole, azulene, and the like, further X ^- include the anion represented by,
^{_{I -, ClO 4 -, BF}} 4 -, PF 6 - , and the like.

The following are specific examples of the iron arene complex.

[0025]

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The pyrylium salt is represented by the following structure.

[0027]

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R _{1 to} R ₉ 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, or an aryl group having 6 to 12 carbon atoms. X
^- represents an anion. Examples of the alkyl group having 1 to 9 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, isooctyl, and nonyl groups.
Further, as the alkenyl group having 1 to 9 carbon atoms, propenyl,
Isopropenyl, butyrenyl, isobutylenyl, hexenyl, octynyl, isooctynyl, nonylyl group and the like; and the alkoxy group having 1 to 9 carbon atoms includes methoxy, ethoxy, butoxy, pentoxy, hexoxy, octoxy group and the like; ^- anions and aryl groups having 6 to 12 carbon atoms represented by the iron arene complex X ^-, it is synonymous with an aryl group having 6 to 12 carbon atoms.

The following are specific examples of pyrylium salts, but the present invention is not limited thereto.

[0030]

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Examples of the boron salt include, but are not particularly limited to, the following compounds comprising a boron atom-containing anion portion and a cation portion.

[0032]

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Here, R _{1 to} R ₄ may be the same or different and may be an alkyl group (eg, ethyl, butyl), an aryl group (eg, phenyl, naphthyl), an aralkyl group (eg, benzyl, phenethyl), an alkenyl group (eg, Vinyl, allyl), an alkynyl group (eg, propenyl), a cycloalkyl group (eg, cyclopentyl, cyclohexyl), a heterocyclic group (eg, thienyl, pyridyl),
Each group may further have a substituent. Particularly preferably, at least one of R _{1 to} R ₄ is an aryl group, and at least one is an alkyl group. The aryl group is preferably a phenyl or naphthyl group, and may be substituted with an alkyl group or an alkoxy group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl groups. These alkyl groups may be substituted with halogen atoms, alkoxy groups, hydroxyl groups, cyano groups, phenyl groups and the like. Examples of the cation moiety represented by X ⁺ include a 5A group onium compound such as an alkali metal cation, an ammonium cation, and a phosphonium cation, a sulfonium,
Group 6A onium compounds such as tellurium, dyes and the like can be mentioned. As the dye, a cyanine dye is preferable, and a cyanine dye used for the following infrared absorbing dye is preferably used.

Specific examples of the boron salt are described in, for example, JP-A-64-13142 and JP-A-2-4804, and preferably include compounds having the following structures.

[0035]

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Further, the aluminate complex is represented by the following structure.

[0037]

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At least one of R _{1 to} R ₄ has 3 to 6 carbon atoms.
And at least one is selected from a phenyl group, a benzyl group and an aryloxy group, and the other is selected from an alkyl group, an alkenyl group and an alkoxy group. D ⁺ is a cation. Carbon number 3 ~
Examples of the alkyl group 6 include propyl, isopropyl, butyl, isobutyl, and a tert-butyl group.
Examples of the aryloxy group include phenoxy and naphthoxy groups, and the cation represented by D ⁺ includes:
Dyes and the like can be mentioned, and as the dye, a cyanine dye is preferable, and among them, a cyanine dye used for the infrared absorbing dye is preferably used.

The following are specific examples of the aluminate complex, but the present invention is not limited thereto.

[0040]

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In the positive photosensitive composition of the present invention, a boron salt and an iron arene complex are particularly preferable among the above group A.

In the present invention, at least one of these is used.
However, two or more kinds may be used in combination. The content of these in the positive photosensitive composition of the present invention is preferably 0.5 to 30% by weight, and more preferably 2 to 10% by weight.
% By weight is more preferred.

Description of [Group B] The positive photosensitive composition of the present invention is characterized by having at least one selected from Group B. The group B includes acrylic resins containing a hydrophilic group in the molecule, and phenolic, polyester and polyurethane resins.

The polyurethane resin in the present invention is:
A polymer containing at least one or more repeating units selected from a urethane bond, a urea bond, a burette bond, and an allophanate bond in the main chain. Such a bond is obtained by selecting a reactive group that mainly undergoes an addition reaction with an isocyanate. Is formed. As the diisocyanate compound suitably used in the above reaction, a conventionally known diisocyanate compound can be used without any particular limitation. Specific examples include, for example, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4 '
Aromatic diisocyanates such as -diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate;
Aliphatic diisocyanate compounds such as trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate; Alicyclic diisocyanate compounds such as 1,3- (isocyanatomethyl) cyclohexane;

The polyurethane resin in the present invention may further include a reaction product of three or more diisocyanates, a reaction product of a conventionally known diisocyanate compound and a polyhydric alcohol of three or more, or a isocyanate compound of three or more functions. Are also preferably used.

As such a trihydric or higher polyhydric alcohol, conventionally known compounds can be used without any particular limitation. Examples of such compounds include, for example, glycerin, trimethylolethane, trimethylolpropane, sorbitol, mannitol, glucose and the like. According to the alcohol valency of these compounds, the desired reaction product can be obtained by adding and reacting with 2 moles of isocyanate groups per mole of hydroxyl groups. Examples of polyfunctional alcohols that form a urethane bond by an addition reaction with an isocyanate compound include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octanediol, diethylene glycol, and triethylene glycol;
Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, 1,
Aliphatic polyfunctional alcohols such as 2,6-hexanetriol, conventionally known polyester polyols having a hydroxyl group at the terminal by condensation of dicarboxylic acid and polyhydric alcohol, conventionally known ring-opening polymerization or alkylene oxide of alkylene oxide And polyether polyols added to polyhydric alcohols.

As a method for hydrophilizing a polyurethane resin obtained by reacting them, for example, 1) a tertiary amino acid is added to a urethane prepolymer having an isocyanate group at a terminal obtained by the above addition polymerization. A method of polymerizing with a diol having a tertiary amino group and quaternizing the tertiary amino group, 2) polymerizing the urethane prepolymer with a diol having a tertiary amino group, neutralizing the tertiary amino with an acid, and effecting amine chlorination. 3) A method of polymerizing the urethane prepolymer with a diol having a quaternary salt, 4) A method of polymerizing the urethane prepolymer with diaminophenylcarboxylate and removing the solvent, and 5) a method of preparing the urethane prepolymer. A method of blocking a terminal isocyanate group with a compound such as sodium bisulfite, 6) the urethane prepolymer 7) A method of polymerizing the urethane prepolymer with bis (2-cyanoethylamino) ethane, 8) A method of polymerizing the urethane prepolymer with an alkylene oxide of a long-chain alcohol. And the like. In addition, "Polyurethane Resin Handbook" edited by Keiji Iwata Nikkan Kogyo Shimbun P49
Polyurethane resins useful in the present invention can be obtained by arbitrarily selecting the methods described in 6 to 502 and the like.

Specifically, Takelac W series manufactured by Takeda Pharmaceutical Company Limited (polyester urethane self-emulsifying type W-621, W-6015, W7004, W-51)
1, W-635, XW-76-P15, XW-74-P
6012C, ACW-31H, ACW-54HD, XW
-904-X05, XW-97-W4), Takerack W series (polyester urethane forced emulsification type W-310, W-512), company-made alkoxysilyl group-containing series (polyester urethane self-emulsion type XW-77-X25). , XW-75-X09, XW-7
4-X13, XS-72-V01, XS-72-V0
2, XS-72-V03, XS-72-V04, XS-
72-V05), High-tack series (S-8531, S-8532, S-8533, Toho Chemical Industry Co., Ltd.)
S-8530, S-8529, S-8528, S-62
54, S-6262, B-1306), Kusumoto Kasei Co., Ltd.
NeoRez series (aliphatic polyester urethane R-960, R-962, R-972, R-97)
4, R-9314, R-9320, R-9617, XR
-9621, XR-9624, R-9637, XR-9
679, XR-9699, XR-9770)
eoRez series (aliphatic polyether urethane R
-966, R967, XR-9000, AX-311,
AX-7113), the company's NeoRez series (aromatic polyether urethane R-940, R-9030,
XR-9409, R-9920, XR-7061), NeoRez series (special urethane, aliphatic polycarbonate urethane XU-7015, R-960)
3), iodosol series (9D102, 9D250Z, 9D232Z) manufactured by Kanebouenusc Co., Ltd., and neotan series (polyester urethane UE-1101, UE-1200, UE) manufactured by Toa Gosei Chemical Industry Co., Ltd.
-1300, UE-1402, UE-2103, UE-
2200, UE-2600, UE-2900), the company's Neotan series (polyether urethane UE-54)
04, UE-5600), Takamatsu Yushi Co., Ltd. Enresin series (R-1489, R-1780), Crown Bond series (UA-28, UA-41, U-).
176R, RI-793, RI-623, U-11
3), Dispacoll series (U-42, U-53, KA8481, KA8) manufactured by Sumitomo Bayer Urethane Co., Ltd.
584).

The polyester resin in the present invention refers to a polymer containing a repeating unit of an ester bond in the main chain. Examples of a method for synthesizing a resin having such an ester bond include “polyester resin”. Handbook "
The method described on pages 21 to 28 can be suitably used, and it is produced by introducing a hydrophilic group into the polyester resin prepolymer formed by such a method by an arbitrary method and polymerizing the prepolymer. Specific examples of such a compound include Pesresin A series (manufactured by Takamatsu Yushi Co., Ltd.)
O ₃ R 110,120,121,193,510,6
10,810), Pesresin A series (Hydrophilic group is COOR 210,620,820), Pesresin A series (Hydrophilic group is SO ₃ R ⁺ glycidyl 1)
15G, 124G, 124GH, 193G, 215G,
515G, 615G813GL), Pesresin A manufactured by the company
Series (Hydrophilic group is SO ₃ R ⁺ Si (OR) ₃ 124
S, 115S), plus coat series (water soluble Z-3402, Z-4121, Z-) manufactured by Ryogo Chemical Industry Co., Ltd.
446, Z-461, Z-448, Z-441, Z-4
50, Z-710, Z-711, Z-770, Z-76
6), plus coat series (water-resistant Z-80)
2, Z-3109, Z-3308, Z-857, Z-8
50, Z-802, Z-856, Z-4201, RZ-
27, RZ-50, RZ-56, RZ-105), Vylonal series (MD-120) manufactured by Toyobo Co., Ltd.
0, MD-1220, MD-1250, MD-110
0, MD-1330, MD-1930).

The phenolic resin used in the present invention is obtained by polymerizing phenols having 1 to 3 valences, and the phenolic resin is phenol, cresol, thymol, carvacrol and partially etherified. Guaiacol and the like; divalent as pyrocatechin, resorcin, hydroquinone, orcin and urushiol; and trivalent as pyrogallol, phloroglucin,
Examples thereof include hydroxyhydroquinone and the like, and divalent bisphenol A having two benzene nuclei, naphthol having a naphthalene nucleus, bisnaphthol, anthrol having an anthracene nucleus, anthrahydroquinone and the like.

The acrylic resin having a hydrophilic group in the present invention includes, for example, -CO-OH, -OH,
_{-NH 2, -NHCONH 2, - (} OCH 2 CH 2) - hydrophilic group such as, or _{-SO 3 H, -SO 3 M,} -OSO 3 H,
_{-OSO 3 M, -COOM, -NR 3} X (M: an alkali metal or -NH _4, R: alkyl group, X: halogen) acrylic resins. Having a strong hydrophilic group such as, for example, the following Things can be mentioned.

(1) Monomer having aromatic hydroxyl group:
For example, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, and the like.

(2) Monomer having aliphatic hydroxyl group:
For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate,
6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(3) Monomers having an aminosulfonyl group: for example, m-aminosulfonyl methacrylate,
p-aminosulfonyl methacrylate, m-aminosulfonyl acrylate, p-aminosulfonyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

(4) Monomers having a sulfonamide group: for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

(5) Monomer having amino group: for example, N, N-diethylaminoethyl methacrylate,
N, N-diethylaminoethyl acrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

The positive photosensitive composition of the present invention preferably contains the above-mentioned phenolic resin and polyurethane resin, and particularly preferably a novolak resin obtained by a polycondensation reaction of the above phenolic resin and formalin. Phenol-formalin novolak resin, cresol-formalin novolak resin and the like can be mentioned, and preferably m-cresol-formalin novolak resin, m, p-mixed cresol-formalin novolak resin and the like can be mentioned.

In the present invention, it is sufficient that at least one of the above resins is provided, but two or more of them may be used in combination. The content of these resins in the positive photosensitive composition of the present invention is preferably from 20 to 90% by weight,
~ 70 wt% is more preferred.

Further, as other resin for the binder, maleic acid, its ester compound, styrene, α-alkylstyrene, α-acetoxystyrene, hydroxystyrene, α-alkylhydroxystyrene, α-acetoxyhydroxystyrene or a hydroxyl group thereof is used. Protecting group-substituted compounds or their cyclic analogs which are easily dissociated by acid treatment, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, crotonic acid, itaconic acid, N-substituted maleimide, vinylbenzoic acid, and esterified products of these Homogenized or copolymer, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyethylene terephthalate, acetylcellulose, methylcellulose, ethylcellulose, polyvinylbutyral, chlorinated polyolefin, polyalkylene, poly Aldehyde, polycarbonate, epoxy resins, melamine resins, alkyd resins, modified polyvinyl alcohol alone or in blocks by the combination or graft copolymer or modified product, and the like, are preferably used together with the resin.

In the present invention, it is preferable that at least one infrared absorbing dye is provided outside the frame of the groups A and B. The infrared-absorbing dye can be used without particular limitation as long as it is a dye that absorbs light having a wavelength of 700 nm or more. Dyes are exemplified, and those represented by the following structures are exemplified.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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Examples of the phthalocyanine dyes include EX Color 802K and EX Color 803K (manufactured by Eastman Kodak).

In the present invention, among the above infrared absorbing dyes, cyanine dyes are particularly preferably used.

In the present invention, it is preferable to contain a radical generator represented by an organic peroxide. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, acetyl peroxide, and propionyl. Peroxide, isobutyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl, decanoyl peroxide, uranoyl peroxide,
Diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and acetylcyclohexanesulfonyl peroxide;
t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2 , 5-dimethyl-2,5-di (t
tert-butylperoxy-3,3,5-trimethyl)
Cyclohexane, n-butyl-4,4'-bis (ter
peroxyketals such as t-butylperoxy) butane, tert-butylperoxyacetate, tert
-Butylperoxypivalate, tert-butylperoxyoctoate, tert-butylperoxy-
3,5,5-trimethylhexanoate, tert-butylperoxybenzoate, di-tert-butylperoxyphthalate, tert-butylperoxyisophthalate, tert-butylperoxylaurate,
Alkyl peresters such as 2,5-dimethyl-2,5-dibenzoylperoxyhexane, di-2-ethylhexylperoxydicarbonate, di-isopropylperoxydicarbonate, di-sec-butylperoxycarbonate, -N-propylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis- (4-tert-butylcyclohexyl) Examples include peroxydicarbonates such as peroxydicarbonate, and water-soluble peroxides represented by succinic peroxide.

In the present invention, it is particularly preferable to use an organic peroxide represented by the following structure.

[0072]

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In the present invention, other than the above-mentioned organic peroxides, for example, onium salts can be used. Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts and stannonium salts. JP-B-55-39162, JP-A-59-1402.
No. 3 and "Macromoleu
les), Vol. 10, p. 1307 (1977). As the iodonium salt, a diaryliodonium salt can be preferably used. For example, diphenyliodonium salt, ditolyliodonium salt, phenyl (pt
tert-butylphenyl) iodonium salt, bis (p-
Chloride such as cyanophenyl) iodonium salt, bromide, boron tetrafluoride, boron hexafluoride, phosphorus hexafluoride, arsenic hexafluoride, antimony hexafluoride, perchlorate, benzenesulfonate , P-toluenesulfonate and the like.

Also, an aromatic compound can be added.
JP-A-55-127550, JP-A-60-20243
2,4,5- represented by the following structure described in No. 7, etc.
Triarylimidazole-based dimers may be mentioned.

[0075]

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Other radical generators that can be used in combination include:
Triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104,
JP-A-59-1504 and JP-A-61-243807
Organic peroxides described in JP-B-43-23684,
44-6413, 47-1604 and USP
No. 3,567,453, U.S. Pat.
SP2,848,328, USP2,852,379
Compounds and organic azide compounds described in US Pat. No. 2,940,853, JP-B-36-22062 and JP-B-37-1310.
No. 9, No. 38-18015 and Japanese Patent Publication No. 45-9610
Orthoquinone diazides described in JP-B-55-39
No. 162, JP-A-59-14023 and "Macromolules, Vol. 10,
Various onium compounds described on page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, EP 109,851,
No. 126,712, "Journal of Imaging Science" (J. Imag. Sci.), No. 3
Vol. 0, p. 174 (1986), a metal allene complex, an (oxo) sulfonium organoboron complex described in Japanese Patent Application Nos. 4-56831 and 4-89535,
The titanocenes described in 1-101197, "Coordination Chemistry Review (Coordina)
Tion Chemistry Review), No. 8
4, pp. 85-277, 1988, "
And organic halogen compounds described in US Pat. Further, the boron salt in [Group A] of the present invention can also be used.

The positive photosensitive composition of the present invention can be provided as a photosensitive layer on a support having a hydrophilic surface together with a solvent described below.

As the support having the hydrophilic surface, for example, the above-mentioned metal thin film is laminated or vapor-deposited on a metal plate such as aluminum, stainless steel, chromium, nickel or the like, for example, a plastic film such as polyester film, polyethylene film or polypropylene film. thing,
For example, a polyester film, a vinyl chloride film, a nylon film, or the like, which has been subjected to a hydrophilic treatment on its surface, or the like may be used. As such a method for hydrophilizing a plastic film, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, provision of a water-soluble resin layer, and the like are preferably used. For use as a photosensitive lithographic printing plate, an aluminum plate having a grained surface, anodized, and sealed as a support is particularly preferred.

Examples of the graining method include a mechanical method and an electrolytic etching method.

Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The above-mentioned various methods can be used alone or in combination depending on the composition of the aluminum material and the like.

Preferred is a method using electrolytic etching. The electrolytic etching is performed in a bath containing one or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous solution of an alkali or an acid to neutralize and wash with water.

The anodic oxidation treatment is carried out by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid or the like as an electrolytic solution, and using an aluminum plate as an anode for electrolysis. The amount of oxide coating formed is 1 to 50 mg / d
m ² is appropriate, and preferably 10 to 40 mg / dm ² . This oxide coating amount is determined, for example, by coating an aluminum plate with a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 ml, chromium oxide:
20 g dissolved in 1 liter of water) to dissolve the oxide film and determine the weight change before and after dissolution of the coating on the plate.

Examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to an undercoating treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconic acid.

The contact angle of the hydrophilic surface with water is not more than 60 degrees, more preferably not more than 40 degrees. The thickness of the support is about 50 to 1000 μm, preferably 75 to 500 μm.
It is in the range of μm.

In order to provide the photosensitive layer on the hydrophilic surface of the support, the photosensitive composition may be dissolved in an appropriate solvent, applied and dried. Examples of the solvent include water, alcohols (eg, methanol, ethanol, propanol, diacetone alcohol), cellosolves (eg, methyl cellosolve,
Ethyl cellosolve, propylene glycol monoethyl ether), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-2-butanone, diethyl ketone), esters Solvents (eg, methyl lactate, ethyl acetate, butyl acetate), ethers (eg, tetrahydrofuran, dioxane), chlorine solvents (eg, chloroform, trichloroethylene), amide solvents (eg, dimethylformamide, N-methylpyrrolidone), dimethyl sulfoxide And the like. One of these solvents or a mixture of two or more thereof is used in accordance with the solution or dispersion.

The coating is performed by a gravure roll coating method,
Conventionally known methods such as an extrusion coating method, a wire bar coating method, and a roll coating method can be employed. The thickness of the photosensitive layer is usually 0.2 to 10.0 μm, preferably 0.5 to 10.0 μm.
５5.0 μm.

A protective layer can be provided on the photosensitive layer if necessary. The protective layer is made up of vinylidene chloride, ethylene-poval copolymer (Eval), polyvinyl alcohol, polyvinylpyrrolidone, gelatin, glue, casein,
Solvent dissolution of resins (preferably polyvinyl alcohol) such as hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethyl starch, gum arabic, saccharose octaacetate, ammonium alginate, sodium alginate, polyvinylamine polyethylene oxide, polystyrenesulfonic acid, polyacrylic acid, etc. It can be formed by applying a product on a photosensitive layer or laminating a film of polypropylene, polyethylene, polybutadiene, eval, polyvinylpyrrolidone, vinylidene chloride, polycarbonate or the like on the photosensitive layer by a method such as lamination. Also, the protective layer may be provided by transferring the protective layer from a protective layer laminating sheet prepared by applying a solution of the resin on another support to the photosensitive layer. During the application process, an additive such as a surfactant may be added for the purpose of improving applicability.

The thickness of the protective layer is preferably from 2 to 100 μm when using a film, and about 0.2 to 10 μm, preferably from 1.0 to 2.0 μm when provided by coating.
It is.

At the time of exposure, a laser light source may be used as a light source for light rays in the visible to near infrared region, for example, a semiconductor laser, a YAG laser, a carbon dioxide laser, a He gas laser.
-Ne laser or the like can be preferably used. A light emitting diode (LED) can be used as an exposure light source. LEDs and semiconductor lasers that are easy to use as an array in which a plurality of light emitting elements are integrated are LEDs and semiconductor lasers. Among semiconductor lasers, it is preferable to use a so-called single-mode laser diode because it is easy to narrow the exposure diameter to several μm to several tens μm at the focal point without significantly lowering the optical efficiency.

When a light source having a wavelength of about 400 to 550 nm is required, a semiconductor laser or YAG
It is also possible to convert to a half wavelength by combining a laser and an element having a nonlinear optical effect.

The laser scanning method includes cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylinder outer surface scanning, laser exposure is performed while rotating a drum around which a photosensitive lithographic printing plate is wound, and the rotation of the drum is used as a main scan and the movement of laser light is used as a sub-scan. In the cylindrical inner surface scanning, a photosensitive material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a part or all of the optical system is rotated to perform a main scanning in the circumferential direction, and a part of the optical system or Sub-scanning is performed in the axial direction by moving the whole linearly in parallel with the axis of the drum. In the planar scanning, the main scanning of the laser beam is performed by combining a polygon mirror or a galvanometer mirror with an fθ lens or the like, and the sub-scanning is performed by moving the photosensitive material. The outer circumferential surface scanning and the inner circumferential surface scanning are easier to improve the accuracy of the optical system, and are suitable for high-density recording. In the case of scanning the outer circumferential surface, it is easy to increase the scanning speed by increasing the rotation speed of the drum, but the increase in the rotation speed tends to cause charging of the photosensitive material, thereby attracting dust and causing image defects. Have a problem.

In the case of a so-called multi-channel exposure in which a plurality of light-emitting elements are used at the same time, circumferential outer surface scanning is most suitable.

The photosensitive lithographic printing plate is suitably used as a lithographic printing plate which is developed by scanning with a laser beam and then developed.

As a developer used for developing a photosensitive lithographic printing plate, a conventionally known aqueous alkali solution can be used. For example, sodium silicate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, potassium An aqueous solution of an inorganic alkali agent such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, and lithium can be used. or,
Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine And organic alkali agents such as ethylenediamine and pyridine. These alkaline agents are used alone or in combination of two or more.

If necessary, an organic solvent such as an anionic surfactant, an amphoteric surfactant or an alcohol can be added to the developer.

[0096]

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

Example 1 [Preparation of a photosensitive lithographic printing plate] An aluminum plate (material: 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous solution of sodium hydroxide kept at 65 ° C for 1 minute. After performing a degreasing treatment, it was washed with water. The degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute to neutralize, and then washed with water. Next, this aluminum plate was placed in a 0.3% by weight aqueous nitric acid solution at a temperature of 25 ° C.
AC current of 60 A / dm ^{2 at} a current density of 60
After electrolytic surface roughening for 2 seconds, a desmut treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The desmutted roughened aluminum plate was placed in a 15% sulfuric acid solution at a temperature of 25 ° C. and a current density of 10%.
Anodizing treatment was performed for 1 minute under the conditions of Amp / dm ² and voltage 15V, sealing treatment was performed at a temperature of 90 ° C., and further 3
% Of carboxymethylcellulose salt to prepare a support. The following photosensitive solution composition (hereinafter, referred to as photosensitive solution) is applied on the grain support using a wire bar so as to have a dry coating amount of 1.3 g / m ^2, and is heated to 80 ° C. under light shielding. A heat treatment was performed for 2 minutes to form a photosensitive layer (photosensitive layer), thereby preparing a photosensitive lithographic printing plate.

(Photosensitive solution 1) High molecular weight polymer (MMA / AN / BA / MAA / HyPma = 40/20/15/5/20) Mw = 50,000 89 parts Iron arene complex (Exemplified compound 1) 8 parts CY -10 (exemplified cyanine dye) 3 parts manufactured by Nippon Kayaku Co., Ltd. 3 parts MEK / cyclopentanone = 8/2, dissolved in a mixed solvent, and dissolved so that the solid content becomes 10% by weight to prepare a photosensitive solution 1. .

MMA: methyl methacrylate AN: acrylonitrile BA: butyl acrylate MAA: methacrylic acid HyPma: hydroxyphenylamide methacrylate Example 2 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition. Was prepared.

(Photosensitive solution 2) High-molecular polymer (novolak resin: m-cresol / acetone condensate ratio of p-cresol 6/4) Mw = 50,000 80 parts Iron arene complex (exemplary compound 1) 8 parts CY- 10 (exemplified cyanine dye) Nippon Kayaku Co., Ltd. 3 parts ter-butylbenzoic acid-ter-butylphenol-formaldehyde resin (Mw = 2000) 8 parts F-177 (fluorinated surfactant; Dainippon Ink Co., Ltd.) 1 part) MEK / PGM = 1/1 The mixture was dissolved in a mixed solvent of 1/1, and dissolved so that the solid content became 8% by weight to prepare a photosensitive lithographic printing plate.

Example 3 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive Liquid 3) Polyester Emulsion (Pesthresin A-513D, manufactured by Takamatsu Yushi Co., Ltd.) 81 parts Iron arene complex (exemplary compound 1) 8 parts CY-10 (exemplary cyanine dye) Nippon Kayaku Co., Ltd. 3 parts ter-butylbenzoic acid-ter-butylphenol-formaldehyde resin (Mw = 2000) 5 parts F-177 (fluorinated surfactant; manufactured by Dainippon Ink Co., Ltd.) 1 part 1,3,5-tetraacetoxy Methylbenzene (2 parts) was dissolved in a mixed solvent of MEK / PGM = 1/1, and dissolved to a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Example 4 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 4) Urethane emulsion (Takelac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.) 80 parts Iron arene complex (Exemplary compound 1) 8 parts Indoaniline dye (Exemplary compound 1) 2 parts MEK / PGM = 1/1, and dissolved to a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Example 5 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 5) High molecular polymer (MMA / AN / BA / MAA = 60/20/15/5) Mw = 50,000 80 parts Pyrilium salt (exemplary compound 1) 6 parts CY-10 (exemplary cyanine Dye) 2 parts, manufactured by Nippon Kayaku Co., Ltd. Dissolved in a mixed solvent of MEK / PGM = 1/1 and dissolved to a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Example 6 A photosensitive lithographic printing plate was produced in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 6) High molecular weight polymer (novolak resin: m-cresol / acetone condensate ratio of p-cresol 6/4) Mw = 50,000 80 parts Pyrilium salt (exemplary compound 2) 6 parts CY-10 (Exemplary cyanine dye) 2 parts manufactured by Nippon Kayaku Co., Ltd. 2 parts MEK / PGM = dissolved in a mixed solvent of 1/1, and dissolved to a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Example 7 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 7) Polyester emulsion (Pesthresin A-513D, manufactured by Takamatsu Yushi Co., Ltd.) 80 parts Pyrilium salt (Exemplary Compound 3) 6 parts CY-10 (Exemplary cyanine dye) Nippon Kayaku Co., Ltd. 2 parts The mixture was dissolved in a mixed solvent of MEK / PGM = 1/1, and dissolved so that the solid content became 8% by weight to prepare a photosensitive lithographic printing plate.

Example 8 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 8) Urethane emulsion (Takelac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.) 80 parts Pyrilium salt (Exemplary Compound 4) 6 parts EX color 803K (phthalocyanine-based dye) Eastman K 6 parts The mixture was dissolved in a mixed solvent of MEK / PGM = 1/1 and dissolved so that the solid content was 8% by weight to prepare a photosensitive lithographic printing plate.

Example 9 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 9) High molecular weight polymer (MMA / AN / BA / MAA / 4-HBA = 40/20/15/5/20) Mw = 50,000 80 parts Boron salt (Exemplary compound 1) 6 parts CY-10 (exemplified cyanine dye) 2 parts, manufactured by Nippon Kayaku Co., Ltd. 2 parts MEK / PGM = dissolved in a mixed solvent of 1/1, and dissolved to a solid content of 8% by weight to produce a photosensitive lithographic printing plate. did.

4-HBA: 4-hydroxybutyl acrylate Example 10 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 10) High molecular weight polymer (novolak resin: m-cresol / acetone condensate ratio of p-cresol 6/4) Mw = 50,000 80 parts Boron salt (exemplary compound 1) 6 parts CY-10 (Exemplary cyanine dye) 2 parts, manufactured by Nippon Kayaku Co., Ltd. Dissolved in a mixed solvent of MEK / PGM = 1/1 and solid content was 8
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 11 A photosensitive lithographic printing plate was produced in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 11) Polyester emulsion (Pesthresin A-513D, manufactured by Takamatsu Yushi Co., Ltd.) 80 parts Boron salt (Exemplary Compound 1) 6 parts CY-10 (Exemplary cyanine dye) Nippon Kayaku Co., Ltd. 3 parts were dissolved in a mixed solvent of MEK / PGM = 1/1, and dissolved so as to have a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Example 12 A photosensitive lithographic printing plate was produced in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 12) Urethane emulsion (Takelac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.) 80 parts Boron salt (Exemplary Compound 1) 6 parts IR-820B (polymethine dye) manufactured by Nippon Kayaku Co., Ltd. 2 parts The mixture was dissolved in a mixed solvent of MEK / PGM = 1/1, and dissolved so that the solid content became 8% by weight to prepare a photosensitive lithographic printing plate.

Example 13 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 13) High molecular weight polymer (MMA / AN / BA / MAA / HyPma = 40/20/15/5/20) Mw = 50,000 89 parts Boron salt (Exemplary compound 1) 6 parts Squarylium-based Dye (Exemplified Compound 1) 3 parts Dissolved in a mixed solvent of water / acetone = 8/2, solid content is 8
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 14 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 14) High molecular weight polymer (MMA / AN / BA / MAA / HyPma = 40/20/15/5/20) Mw = 50,000 89 parts Aluminate complex (Exemplified Compound 1) 8 parts CY -10 (exemplified cyanine dye) Nippon Kayaku Co., Ltd. 3 parts Water / acetone = 8/2
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 15 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 15) High molecular weight polymer (novolak resin: ratio of m-cresol / acetone condensate of p-cresol 6/4) Mw = 50,000 80 parts Aluminate complex (Exemplary compound 2) 8 parts CY- 10 (exemplary cyanine dye) 3 parts, manufactured by Nippon Kayaku Co., Ltd. 3 parts dissolved in a mixed solvent of water / acetone = 8/2 to obtain a solid content of 8
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 16 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1, except that the photosensitive solution had the following composition.

(Photosensitive Liquid 16) Polyester Emulsion (Pesthresin A-513D, manufactured by Takamatsu Yushi Co., Ltd.) 89 parts Aluminate complex (Exemplary Compound 3) 8 parts CY-10 (Exemplary cyanine dye) Nippon Kayaku Co., Ltd. 3 parts Water / acetone = 8/2
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 17 A photosensitive lithographic printing plate was produced in the same manner as in Example 1, except that the photosensitive solution had the following composition.

(Photosensitive solution 17) Urethane emulsion (Takelac XW-76-P15 manufactured by Takeda Pharmaceutical Co., Ltd.) 89 parts Aluminate complex (Exemplary compound 4) 8 parts NKX1199 (Exemplary Ni complex dye) Nippon Kayaku Co., Ltd. 3 parts dissolved in a mixed solvent of water / acetone = 8/2, and the solid content was 8
It melt | dissolved so that it might become weight%, and produced the photosensitive lithographic printing plate.

Example 18 (Comparative Example) A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 18) High molecular polymer (MMA / AN / BA / MAA / HyPma = 40/20/15/5/20) Mw = 50,000 89 parts Diphenyliodonium.PF ₆ salt 8 parts IR-820B (Polymethine dye) Nippon Kayaku Co., Ltd. 2 parts 2,4,6-tris (trichloromethyl) -S-triazine 8 parts MEK / PGM = 1 wt% dissolved in a mixed solvent of 1/1. To prepare a photosensitive lithographic printing plate.

Example 19 (Comparative Example) A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

(Photosensitive solution 19) Polyamide emulsion (KP-2002, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 89 parts Iron arene complex (Exemplary compound 1) 8 parts CY-10 (Exemplary cyanine dye) Nippon Kayaku Co., Ltd. 3 parts MEK / PGM = dissolved in a mixed solvent of 1/1, and dissolved to a solid content of 8% by weight to produce a photosensitive lithographic printing plate.

Example 20 (Comparative Example) A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution had the following composition.

[0136] (Photosensitive solution 20) polyamide emulsion (Matsumoto Yushi-Seiyaku Co., Ltd. (KP-2002)) 89 parts of diphenyliodonium · PF ₆ salt 8 parts TX-208A (phthalocyanine dye) Konica Corp. 2 parts MEK The mixture was dissolved in a mixed solvent of / PGM = 1/1, and dissolved to a solid content of 8% by weight to prepare a photosensitive lithographic printing plate.

Hereinafter, the group A, the group B and the infrared absorbing dye are shown in a table in a simplified manner.

[0138]

[Table 1]

Iron arsenic: iron arene complex Pyril: pyrylium salt Boron: boron salt Aluminum: aluminate complex Dife: diphenyliodonium PF ₆ salt Mixing: resin in which acrylic and phenol are combined
Fe: Phenol S: Polyester Ure: Polyurethane Ami: Polyamide • Indoor: Indoaniline dye Phthalocyanine: Phthalocyanine dye Polymethy: Polymethine dye Squali: Squalilium dye <Image formation> Semiconductor laser The image was exposed by focusing on the photosensitive layer of the resulting photosensitive lithographic printing plate and performing scanning exposure from the photosensitive side. In this case, after exposure, after passing between a pair of heat rolls heated to 100 ° C., SDR-1 (Konica Corporation)
The photosensitive layer at the exposed portion was eluted by immersing the photosensitive layer at 30 ° C. for 30 seconds using an arbitrary diluent prepared in (1) above, washed with water and dried to prepare an image, and the sensitivity and the resolution of the formed image were confirmed.

Light source: LT090MD, manufactured by Sharp Corp., output: 100 mW, main wavelength: 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch:
The 6 μm image formed portion was evaluated according to the following criteria.

-Sensitivity- An average exposure amount (E: unit) of a photosensitive lithographic printing plate surface on which solid scanning exposure is performed so that an image of 0.5 mm × 0.5 mm is formed at a beam diameter of 4 μm and an image is formed. mJ / c
m ² ) was evaluated on a 5-point scale.

5 ... E≤100 4 ... 100 <E≤250 3 ... 250 <E≤400 2 ... 400 <E≤600 1 ... 600 <E In the present invention, evaluation 3 The above is considered practical and considered as high sensitivity.

-Resolution- The number of resolvable lines per mm (N) when forming an image with an average exposure amount on the surface of a photosensitive lithographic printing plate by setting the scanning exposure to a beam diameter of 4 μm and a scanning pitch of 4 μm is 4 It was rated on a scale.

4 ... 125 = N 3 ... 120≤N <125 2 ... 110≤N <120 1 ... N <110 In the present invention, a rating of 3 or more is practical and the resolution is good. Is assumed to be.

The results obtained are shown in Table 2 below.

[0146]

[Table 2]

As is evident from Table 2, the lithographic printing plate using the positive photosensitive composition of the present invention can form an image with high sensitivity and good resolution due to improvement in developability. In particular, from group A, iron arene complexes, boron salts, B
It can be seen that when phenol-based, polyurethane-based, and cyanine dyes are further selected and combined from the infrared-absorbing dyes from the group, the effects are dramatically improved.
However, it can be seen that, in the case where both the group A and the group B are not used, both the improvement of the sensitivity and the improvement of the resolution cannot be achieved.

[0148]

According to the present invention, high sensitivity can be obtained even at a lower exposure energy, and improvement in developability can be expected. Therefore, the present invention has a remarkably excellent effect that an image having better resolution can be formed.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 61/04 C08L 61/04 67/00 67/00 71/10 71/10 75/04 75/04 G03F 7/00 503 G03F 7/00 503 7/004 503 7/004 503A 506 506 7/023 511 7/023 511 7/029 7/029 (72) Inventor Tatsuichi Maebashi 1 Sakuracho, Hino-shi, Tokyo In-house (72) Inventor Sota Kawakami Konica Corporation, 1 Sakuracho, Hino City, Tokyo

Claims (6)

[Claims] 1. A positive photosensitive composition comprising at least at least one selected from the following group A and at least one selected from group B: [Group A] a) At least one iron arene complex represented by the following formulas (1) to (3): (R ₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms,
2 aryl group, X ^- represents an anion. B) a pyrylium salt of the following structure: (R _{1 to} R ₉ are 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, an aryl group having 6 to 12 carbon atoms, X ⁻ is an anion C) a boron salt, d) an aluminate complex represented by the following structure: (At least one of R _{1 to} R ₄ is an alkyl group having 3 to 6 carbon atoms, and at least one is selected from a phenyl group, a benzyl group and an aryloxy group, and the others are an alkyl group, an alkenyl group and an alkoxy group. And D ⁺ is a cation.) [Group B] an acrylic resin containing a hydrophilic group in the molecule;
And phenolic, polyester and polyurethane resins. 2. The positive photosensitive composition according to claim 1, wherein the boron salt of c) comprises an anion part containing a boron atom and a cationic dye part. 3. The positive photosensitive composition according to claim 2, wherein said cationic dye part contains a cyanine dye. 4. The positive photosensitive composition according to claim 1, further comprising a novolak resin. 5. The positive photosensitive composition according to claim 1, which comprises at least one infrared absorbing dye. 6. The positive photosensitive composition according to claim 1, comprising at least one organic peroxide.