JP2002265806A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition capable of being developed with an aqueous alkaline solution, presenting an abrasion-resistant plane printing plate having a strong printing resistance, having a wide range of developing conditions without giving stains during printing, excellent in coupling performance, suitable for ball pen writing, having sensitivity and stability during preservation and little deterioration in performances such as sensitivity after exposure and the like. SOLUTION: In the photosensitive composition containing a water insoluble and aqueous alkaline solution-soluble vinyl polymer-based high molecular compound and o-naphthoquinone diazide, the vinyl polymer-based high molecular compound is a copolymer containing at least one species of each of (A) a monomer compound having an active imino group expressed by a specific general formula and (B) a monomer unit derived from a monomer compound having an onium group expressed by a specific general formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. More specifically, it consists of a polymer compound with excellent abrasion resistance and chemical resistance, has a wide range of development conditions, is excellent in coupling performance, ballpoint pen suitability, sensitivity, storage stability, and develops after a long time after exposure. The present invention relates to a photosensitive lithographic printing plate capable of performing an efficient plate-making operation with little change in sensitivity over time.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. However, due to the properties of the novolak type phenol resin used as the main component, the adhesion to the base plate is poor, the film is brittle, the abrasion resistance is poor, and the printing durability when used for lithographic printing plates is not sufficient. There was a point to be improved, and there was a limit in application. In order to solve such a problem, various polymers have been studied as binders. For example,
The polyhydroxystyrene or hydroxystyrene copolymer described in JP-A-52-41050 certainly has improved film properties, but has the disadvantage of poor abrasion resistance. On the other hand, JP-A-63-226641 describes a positive-type photosensitive composition using an alkali-soluble polymer having an active imino group as a binder.
It is disclosed that adhesion to a substrate and abrasion resistance are improved. However, there is a problem that stains easily occur during printing. In addition, when a positive photosensitive lithographic printing plate containing an o-naphthoquinonediazide compound as a photoreceptor is generally developed with an alkaline developing solution containing water as a main solvent, the o-naphthoquinonediazide compound is produced in a halftone image area. In some cases, the decomposition product and unreacted product of the compound may cause a coupling reaction to form a red dye. If the dye remains on the support, there arises a problem that the erasability of the image area is reduced and the workability when trying to erase an unnecessary image is reduced. In addition, when performing so-called multi-sided printing in which a plurality of original films are printed one after another on a photosensitive lithographic printing plate at different positions, the position of the original may be marked on the photosensitive layer for alignment between the original films. However, there is a problem that the solvent of the oil-based ballpoint pen ink, which is usually used as a writing instrument for this marking, is eroded and the photosensitive layer is dissolved. In particular, in the case where the marked portion is an image portion, if development processing is performed as it is, the photosensitive layer at the mark portion of the image portion is removed, and a failure occurs in which a mark mark is reproduced on a printed matter at the time of printing. For this reason, a photosensitive composition having the property of being hardly corroded by the ink of a ballpoint pen (hereinafter referred to as “ballpoint pen suitability”) is also desired. In general, as a method of preparing a positive photosensitive lithographic printing plate, a lithographic film is exposed by overlapping with a photosensitive layer of a lithographic printing plate material, and the exposed material is developed with a developing solution to form a printing plate. That is being done. In this plate making process, the time from exposure to development is not uniform, and if it is long, development may be performed several days after exposure. However, there has been a problem that the sensitivity at the time of development varies greatly due to a long time lapse after exposure, and a normal printed matter cannot be obtained. Further, many of these photosensitive materials do not have sufficiently satisfactory performances such as short shelf life and low sensitivity to actinic rays.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition which can be developed with an aqueous alkaline developer, has excellent abrasion resistance, and provides a lithographic printing plate having high printing durability. It is. Further, the object of the present invention is to develop a wide range of developing conditions, not to generate stains during printing, to have excellent coupling performance, ballpoint pen suitability, sensitivity, storage stability, and a slight decrease in performance such as sensitivity fluctuation with time after exposure. It is to provide a photosensitive composition that gives a lithographic printing plate. It is a further object of the present invention to provide a photosensitive composition having good adhesion to a substrate, providing a flexible film, and having excellent solubility in an organic solvent.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed a positive-acting photosensitive composition characterized by containing a vinyl polymer polymer compound insoluble in water and soluble in an alkaline aqueous solution and o-naphthoquinonediazide. In the composition, the vinyl polymer-based polymer compound is represented by the following general formula (I) or (II):
And (B) a copolymer containing at least one monomer unit derived from a monomer compound having an onium group represented by the following general formulas (III) to (V): It has been found that these objects can be achieved by a photosensitive composition characterized by the following, and the present invention has been achieved.

[0005]

Embodiments of the present invention will be described below in detail. The water-insoluble and vinyl polymer-soluble polymer compound soluble in an alkaline aqueous solution used in the present invention refers to (A) a compound represented by the general formula (I) or (II) having an active imino group:
And at least one of the monomer compounds represented by the following general formulas (III) to (V) having an onium group (B) in a suitable solvent using a known polymerization initiator. It is a polymer compound obtained by polymerization. In the present invention, the monomer compound (A) having an active imino group is a compound represented by the general formula (I) or (II).

[0006]

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Wherein A represents a hydrogen atom, a halogen atom or an alkyl group. B is a single bond, an alkylene group,
Represents a phenylene group, a substituted alkylene group or a substituted phenylene group. X ¹ is,

[0008]

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[0009] X ² is,

[0010]

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Wherein R ¹ represents an optionally substituted alkyl group, cycloalkyl group, phenyl group or naphthyl group.

[0012]

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(Wherein, E and E ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group; F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group. X ³ and X ⁴ are each independently

[0014]

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[0015] )

A in the general formula (I) is a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom or a methyl group. B is a single bond, an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group, and more preferably a single bond or a phenylene group. X ¹ is,

[0017]

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Which is more preferably

[0019]

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## EQU1 ## X ² is,

[0021]

Embedded image Represents, more preferably,

[0022]

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## EQU1 ## R ¹ represents an alkyl group which may have a substituent, a cycloalkyl group, a phenyl group, or a naphthyl group, more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, And may be an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, or a naphthyl group.

E and E 'in formula (II) each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; More preferably, it is a hydrogen atom. F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group, more preferably a single bond or an alkylene group having 1 to 4 carbon atoms, further preferably a single bond or a methylene group. X ³ and X ⁴
Are independent of each other,

[0025]

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Which is more preferably

[0027]

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Specific examples of the monomer compound represented by the general formula (I) or (II) include the following compounds.

[0029]

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The content of the monomer unit derived from the compound (A) which can be suitably used as a monomer compound of a vinyl polymer type polymer compound which is insoluble in water and soluble in an alkaline aqueous solution is as follows:
1 to 60 mol%. Preferably it is 10-35 mol%. 1
If it is less than mol%, it may cause poor development or contamination, and
If the amount exceeds mol%, development flow or deterioration of printing durability is caused, which is not suitable. The compound (B) having an onium group is a compound represented by the general formula (III), (IV) or (V).

[0031]

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(Wherein J represents a single bond or a divalent linking group)
K represents a single bond, an aromatic group or a substituted aromatic group.
And M represents a single bond or a divalent linking group. However, J and
And K are not simultaneously a single bond. Y₁Is the group V of the periodic table
Represents an atom, Y_TwoRepresents an atom belonging to Group VI of the periodic table. Z^-Is
Represents a counter anion. R^TwoIs a hydrogen atom, an alkyl group or
Represents a halogen atom. R^Three, R^Four, R^Five, R⁷Is German
May have a hydrogen atom or an optional substituent
Represents an alkyl group, an aromatic group or an aralkyl group;
⁶Represents an alkylidyne group or substituted alkylidyne,
R^ThreeAnd R^FourOr R⁶And R ⁷Each combine to form a ring
You may. When K represents a substituted aromatic group, the substituent is
In the formulas (II), (III) and (IV), the following (ii),
It may be a group represented by the formulas (iii) and (iv). 2 or more
Each substituent is the same when substituted by
But they may be different. In the formulas (ii) to (iv), M, Y₁,
Y_Two, Z and R^Three~ R⁷Each group is as defined above.
You.

[0033]

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Formulas (II), (III) and (IV)
Of the compounds which are particularly preferably used in the present invention.
Means that J represents -COO- or -CONH-, and K is
Represents a phenylene group or a substituted phenylene group,
The group is a hydroxyl group, a halogen atom or an alkyl group. M
Is an alkylene group having 1 to 4 carbon atoms or a molecular formula of CnH2n
Divalent series represented by O, CnH2nS or CnH2n + 1N
Represents a linking group. Here, n represents an integer of 1 to 12. Y₁
Represents a nitrogen atom or a phosphorus atom;_TwoRepresents a sulfur atom
Represent. Z^-Is a halogen ion, PF₆ ^-, BF_Four ^-Or R⁸
SO_Three ^-Represents (R ⁸Is an alkyl which may have a substituent
Represents a kill group, an aromatic group, or an aralkyl group. ). R
^TwoRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R^Three, R^Four, R^Five, R⁷Are each independently a hydrogen atom or
Alkyl having 1 to 10 carbon atoms optionally having substituent (s)
R, an aromatic group or an aralkyl group;⁶Is charcoal
Alkylidyne group of 1 to 10 or substituted alkylidyne
Represents, R^ThreeAnd R^FourOr R⁶And R⁷Is a ring
May be formed. When K represents a substituted aromatic group,
The substituents are the following in the formulas (II), (III) and (IV), respectively.
(Ii), (iii) and (iv).
No. When substituted by two or more substituents,
The substituents may be the same or different. In formulas (ii) to (iv),
M, Y₁, Y_Two, Z and R^Three~ R⁷Each group of is defined above
It is on the street.

[0035]

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Among the components having an onium group, J is particularly preferably a single bond, K represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. . M represents an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. Z ^- is a chloride ion or R ⁸ SO ₃ ^- represents a.
R ² represents a hydrogen atom or a methyl group. R ⁸ is optionally bonded to a substituted alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or an aralkyl group, more preferably a methyl group and toluyl group. Specific examples of the compound having an onium group are shown below. However, the present invention is not limited to this specific example.

(Specific examples of compounds having an onium group)

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The content of the monomer unit derived from the compound (B) having an onium group which can be suitably used as a monomer compound of a vinyl polymer type polymer compound which is insoluble in water and soluble in an alkaline aqueous solution is 1 to 50 mol%. . If it is less than 1 mol%, it causes poor development or staining, and if it exceeds 50 mol%, it causes the development flow and is unsuitable.

The polymer compound used in the present invention is
(A) a compound having an active imino group and (B) a compound having an onium group may each be one or more copolymers, but preferably contains one or more polymerizable unsaturated bonds, In addition, it is a copolymer with one or more compounds not containing an active imino group represented by the general formula (I) or (II) and an onium group represented by the general formula (III), (IV) or (V).

An active imino group containing such a polymerizable unsaturated bond and represented by the general formula (I) or (II) and an onium represented by the general formula (III), (IV) or (V) Examples of the compound containing no group include acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, croton esters and the like. And a compound having a polymerizable unsaturated bond. Specifically, for example, acrylates, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic Amyl acid, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate , Benzyl acrylate, methoxy benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg phenyl acrylate, etc.) ): Methacrylic esters, for example,
Alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Isopropyl methacrylate, amyl methacrylate,
Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate,
Pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc., aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides such as acrylamide, N-alkylacrylamide (the alkyl group As the number of carbon atoms is 1 to 1
There are 0, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, benzyl group and the like. ), N-arylacrylamides (for example, the phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.), N, N-dialkylacrylamide (the alkyl group includes carbon Those having 1 to 10 atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-arylacrylamide (as the aryl group, for example, phenyl group etc.) ), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like: methacrylamides such as methacrylamide, N-alkylmethacrylamide ( The alkyl group has 1 to 10 carbon atoms. Things, such as methyl group, ethyl group, t- butyl group, ethylhexyl group,
Examples include a hydroxyethyl group and a cyclohexyl group. ), N-aryl methacrylamide (the aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diarylmethacrylamide (the aryl group includes a phenyl group and the like), N-hydroxyethyl-N-
Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, etc .: Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, palmitin) Allyl acid, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc., allyloxyethanol, etc .: vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxy) Ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2
-Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ether (for example, vinyl phenyl ether) , Vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.): vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, and vinyl Diethyl acetate, vinyl valate, vinyl caproate, vinyl Chloroacetate, vinyldichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, vinylphenylacetate, vinylacetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorbenzoate Vinyl acid, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .: styrenes such as styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, Decyl styrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (for example, methoxystyrene, 4-methoxy-3-methylstyrene,
Dimethoxystyrene, halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4)
-Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): crotonic esters, for example, alkyl crotonates (such as butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.): dialkyl itaconates (For example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): dialkyls of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): acronitrile, methacrylonitrile, etc.
Of these compounds having a polymerizable unsaturated bond, those preferably used are methacrylic esters, acrylic esters, methacrylamides, acrylamides,
Acrylotrile, methacrylonitrile, methacrylic acid,
Acrylic acid, particularly preferably used are acrylonitrile and methacrylonitrile.

One or more of these may be used, and the content of these copolymer components preferably used is 0%.
8080 mol%, particularly preferably 30 to 80 mol%. One or more of these compounds having a polymerizable unsaturated bond, one or more of a low molecular compound represented by the general formula (I) or (II) and one or more of a (meth) acrylate having a poly (oxyalkylene) chain. As the polymer, any of a block body, a random body, a graft body and the like can be used.

Examples of the solvent used for synthesizing such a high molecular compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-glycol.
Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-
Examples include dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents are used alone or in combination of two or more.

The molecular weight of the polymer compound of the present invention is preferably 2,000 or more by weight average and 1,000 or more by number average. More preferably, the weight average is in the range of 5,000 to 300,000, and the number average is in the range of 2,000 to 250,000. Further, the polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 10. The polymer compound of the present invention may contain an unreacted monomer. In this case, the proportion of the monomer in the polymer compound is desirably 15% by mass or less. The polymer compound of the present invention may be used alone or as a mixture. The content of these high molecular compounds contained in the photosensitive composition is about 3 to 95.
%, Preferably about 5 to 85% by weight.

The o-naphthoquinonediazide compound used in the present invention is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403. preferable. Other suitable orthoquinonediazide compounds include U.S. Patent Nos. 3,046,120 and 3,188,2
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in US Pat. Other useful o-naphthoquinonediazide compounds have been reported in many patents and are known. For example, JP-A-47-5303,
8-63802, 48-63803, 48-96575, 49-49
No. 38701, No. 48-13354, No. 37-18015, No. 41-
No. 11222, No. 45-9610, No. 49-17481, U.S. Pat.No. 2,797,213, No. 3,454,400, No. 3,544,323
No. 3,573,917, No. 3,674,495, No. 3,785,82
No. 5, UK Patent Nos. 1,227,602, 1,251,345,
Examples thereof include those described in the specifications such as 1,267,005, 1,329,888, 1,330,932, and German Patent 854,890.

Particularly preferred o-naphthoquinonediazide compounds in the present invention are compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402 and JP-A-58-150948.
No. 58-203434, No. 59-165053, No. 60-121445,
No. 60-134235, No. 60-163043, No. 61-118744, No. 62-
No. 10645, No. 62-10646, No. 62-153950, No. 62-178562
No., Japanese Patent Publication No. 8-14696, U.S. Pat.No. 3,102,809,
No. 3,126,281, No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,210, No. 4,639,40
Examples described in each gazette or specification such as No. 6 can be cited.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound,
Preferably, the reaction is carried out at 1.0 to 1.0 equivalent. Also obtained o-
The naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts.
The proportion of the compound converted with the diazonaphthoquinone sulfonic acid ester in this mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. is there. The amount of the o-naphthoquinonediazide compound in the photosensitive composition of the present invention is 10 to 50% by mass, more preferably 15 to 40% by mass.
It is.

In the composition of the present invention, in addition to the above-mentioned polymer compound, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol ( a known alkali-soluble polymer such as cresol formaldehyde resin such as mixed formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. Compounds can be included. These alkali-soluble polymer compounds have a weight average molecular weight of 500
Those having a number average molecular weight of 200 to 60,000 with a molecular weight of up to 20,000 are preferred. Such an alkali-soluble polymer compound is used in the total composition.
It is used in an addition amount of 70% by mass or less.

Further, as described in U.S. Pat. No. 4,123,279, phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferred to use a condensate of the above in combination in order to improve the oil sensitivity of the image. It is preferable to add a cyclic acid anhydride, a phenol, or an organic acid to the photosensitive composition of the present invention in order to increase sensitivity. U.S. Pat.No. 4,115,128 as a cyclic acid anhydride
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6
-Endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like.

As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4,4 "-trihydroxy-triphenylmethane, 4,4 ', 3", 4 " -Tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane and the like can be mentioned. As organic acids, JP-A-60-88942, JP-A-2-96
No. 755, etc. There are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like,
Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-
Undecanoic acid, ascorbic acid and the like.

The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by mass, more preferably from 0.1 to 5% by mass. Further, in the photosensitive composition of the present invention, in order to widen the development latitude, JP-A-62-251740 and non-ionic surfactants as described in JP-A-4-68355. Agent, JP-A-59-121044, registration 2639
Amphoteric surfactants such as those described in 741 can be added. Specific examples of the nonionic surfactant include polyoxyethylene polyoxypropylene block polymer, sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, and Amogen K (trade name, manufactured by Daiichi Kogyo Co., Ltd., N-tetradecyl-N). , N-betaine type), 2-alkyl-N-carboxyethyl-N
-Hydroxyethyl imidazolinium betaine, levon
15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkyl imidazoline). Among them, it is particularly preferable to add a polyoxyethylene polyoxypropylene block polymer. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is 0.05 to 15% by mass.
Is more preferable, and more preferably 0.1 to 5% by mass.

In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, and other fillers can be added. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified.
Specifically, o-naphthoquinonediazide-4- described in JP-A-50-36209 and JP-A-53-8128 are disclosed.
Combinations of sulfonic acid halides and salt-forming organic dyes and JP-A Nos. 53-36223, 54-74728, 60-3626, and 61
And combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-143748, JP-A-61-151644 and JP-A-63-58440. Such trihalomethyl compounds include oxadiazole-based compounds and triazine-based compounds, both of which are excellent in stability over time and give clear print-out images, but have an oxide film amount of 1.0 g / m ² or more. In the case of a photosensitive lithographic printing plate using, the residual color after development is particularly deteriorated. The invention is particularly effective when a photosensitive composition containing such a compound is used, and a lithographic printing plate having almost no residual color can be obtained.

Other dyes besides the above-mentioned salt-forming organic dyes can be used as image coloring agents. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312,
Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS,
Oil black T-505 (above, manufactured by Orient Chemical Co., Ltd.) Victoria Pure Blue, Crystal Violet (CI42555), Ethyl Violet (CI4260)
0), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42000),
Methylene blue (CI52015) and the like. Dyes described in JP-A-62-293247 are particularly preferred.

The photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used here, γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2- Propyl acetate, toluene, ethyl acetate,
Methyl lactate, ethyl lactate, dimethylsulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol,
There are acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents are used alone or as a mixture. And the concentration (solid content) in the above components
Is 2 to 50% by mass. The amount of coating varies depending on the application, but for example, in the case of a photosensitive lithographic printing plate, it is generally preferred that the solid content be 0.5 to 3.0 g / m ² . As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

In the photosensitive composition of the present invention, a surfactant for improving coating properties, for example, JP-A-62-1709.
A fluorine-based surfactant as described in JP-B-50 can be added. The preferred addition amount is 0.01 to 1% by mass of the total photosensitive composition, more preferably 0.05 to 0.5% by mass.
It is. When a lithographic printing plate is produced using the photosensitive composition of the present invention, the support is preferably an aluminum plate. Aluminum plates include pure aluminum and aluminum alloy plates. 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, or nickel is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The aluminum plate is subjected to a surface treatment as required. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation treatment is preferably performed. Also, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, U.S. Pat.
As described in the specification of Japanese Patent No. 1,461, an aluminum plate subjected to an anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment may be, for example, an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. It is carried out by passing a current through an aluminum plate as an anode. U.S. Patent No.
Electrodeposition of silicate as described in 3,658,662 is also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive layer. It is done to improve.

Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used. As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, particularly, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in JP-A-55-137793 discloses oil-sensitive images. Is preferred because of its strong adhesion to the support. Graining by the above-mentioned method has a center line surface roughness (Ha) of 0.3 to 1.
It is preferable that the application is performed within a range of 0 μ.

The aluminum plate thus grained is washed with water and chemically etched as required. The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary films on the etched surface.

Most preferably, these etching agents are used so that the dissolution rate of the aluminum or alloy used is from 0.3 g to 40 g / m ² per minute of immersion time, when the concentration and temperature are set. However, it may be higher or lower. The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying the etching solution to the aluminum plate, and is preferably processed so that the etching amount is in the range of 0.5 to 10 g / m ² . As the etching agent, it is preferable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. The acids used for desmutting are nitric acid, sulfuric acid, phosphoric acid,
Chromic acid, hydrofluoric acid, hydrofluoric acid and the like are used.

The etched aluminum plate is
Washed and anodized as needed. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or the like or a combination of two or more of them, aluminum is supported. An anodized film can be formed on the body surface.
The anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be unconditionally determined. Generally, however, the concentration of the electrolytic solution is 1 to 80% by mass, the liquid temperature is 5 to 70 ° C, and the current density is 0.5 to 0.5%. 60
Amps / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, the method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768, U.S. Pat.
The method of anodizing in a low concentration of sulfuric acid as described in 1,619 and the method of anodizing phosphoric acid as an electrolytic bath described in U.S. Pat. No. 3,511,661 are preferred.

The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilization treatment, if necessary. A preferred example is US Pat. No. 2,714,066.
And alkali metal silicates such as those disclosed in U.S. Pat.No. 3,181,461, such as aqueous sodium silicate or potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. There is a method of treating with polyvinyl sulfonic acid as described above.

An undercoat layer made of a water-soluble compound can be provided on the aluminum plate which has been roughened as described above, anodized and, if necessary, subjected to a hydrophilic treatment. Examples of such water-soluble compounds include Japanese Patent Publication No. Sho 57-1
No. 6349 discloses a combination of a water-soluble metal salt and hydrophilic cellulose (for example, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose), and polyacrylamide disclosed in U.S. Pat. No. 3,511,661. Polyvinyl phosphonic acid disclosed in JP-B-46-35685, JP-A-60-149491
And amino acids and salts thereof (Na
Salts, alkali metal salts such as K salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), JP-A-60-232998
Amines having a hydroxyl group and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in
63-165183 discloses a compound having an amino group and a phosphonic acid group or a salt thereof, and JP-A-3-261592 discloses (a) an amino group and (b) a phosphonic acid group, and a phosphinic acid. Compounds having one group or one phosphate group or salts thereof, and aliphatic or aromatic phosphonic acids or phosphinic acids disclosed in JP-A-5-246171 or salts thereof, and the like. Above all, Japanese patent application
The compounds disclosed in JP-A-2-59592 and JP-A-5-246171 are particularly preferred. Such water-soluble primer layer compounds preferably provided in the range of 1mg / m ² ~80mg / m ² in solid content.

The surface of the photosensitive layer provided as described above is preferably matted in order to reduce the time for evacuation and prevent blurring during contact exposure using a vacuum printing frame. Specifically, JP-A-50-125805, JP-B-57-65
No. 82, a method of providing a mat layer as described in each of JP-A-61-28986, a method of heat-fusing a solid powder as described in JP-B-62-62337, and the like. .

The developer for the photosensitive composition of the present invention comprises:
Alkaline aqueous solutions substantially free of organic solvents are preferred, specifically sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Aqueous solutions such as ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia and the like are suitable, and their concentration is 0.1 to 10% by mass, Preferably, it is added so as to be 0.5 to 5% by mass.

Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, sodium silicate and the like is preferable since stains during printing hardly occur.
When the composition of the alkali silicate is [SiO ₂ ] / [M] = 0.
5 to 2.5 (where [SiO ₂ ] and [M] indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively),
And developer containing SiO ₂ 0.8 to 8 wt% is preferably used. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, and thiosalicylic acid can be added to the developer.
The preferred content of these compounds in the developer is 0.
It is 002 to 4% by mass, preferably 0.01 to 1% by mass.

As a developer for the photosensitive lithographic printing plate of the present invention, an alkaline aqueous solution having a pH of 12.5 or less can be used.
More preferably, an alkaline aqueous solution having a pH of 8 to 11 is used. Examples of the basic compound used to adjust the pH value include sodium tribasic phosphate, potassium tribasic phosphate, ammonium tribasic phosphate, dibasic sodium phosphate,
Phosphates such as potassium diphosphate and dibasic ammonium phosphate, carbonates such as ammonium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and borate Borates such as ammonium acid, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and ammonium hydroxide. Particularly preferred are combinations of carbonate and bicarbonate. These may be used alone or as a mixture.

As another basic compound, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoetalamine, diethanolamine, triethanolamine, monoisopropanolamine And water-soluble organic amine compounds such as diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like. Among them, monoethanolamine, diethanolamine, triethanolamine and the like are particularly preferable, and may be used in combination with an inorganic alkali metal salt or the like. The concentration of these basic compounds in the aqueous solution is used in the range of pH 12.5 or less, more preferably pH 8 to 11, as described above, but is generally in the range of 0.05 to 10% by mass. You can choose.

In the developer, anionic surfactants and amphoteric surfactants described in JP-A-50-51324 and JP-A-59-84241 are disclosed. JP-A-60-111246 and JP-A-55-959 by including at least one of nonionic surfactants as described in JP-A-60-213943 and the like.
No. 46, No. 50-142528, by including a polymer electrolyte, the wettability to the photosensitive composition is increased, and the development stability (development latitude) is increased. And it is preferably used.
The addition amount of such a surfactant is preferably 0.001 to 2% by mass, particularly preferably 0.003 to 0.5% by mass. Further, as the alkali metal of the alkali silicate, it is preferable that potassium is contained in an amount of 20 mol% or more in all the alkali metals because less insoluble matter is generated in the developer, more preferably 90 mol% or more.
Most preferably, it is 100 mol%. Further, in the developer used in the present invention, some organic solvents such as alcohols and chelating agents described in JP-A-58-190952, as described in JP-B-1-30139. An antifoaming agent such as a metal salt or an organic silane compound can be added.

Light sources used for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp and a metal halide lamp. A photosensitive lithographic printing plate using the photosensitive composition of the present invention is disclosed in JP-A-54-8002.
It is needless to say that the plate-making process may be carried out by the methods described in JP-A Nos. 55-115045 and 59-58431. That is, after development processing, washing with water and then desensitization processing,
Alternatively, desensitization treatment may be performed, treatment with an aqueous solution containing an acid, or treatment with an aqueous solution containing an acid, followed by desensitization treatment. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity is reduced, the processing capacity may be restored by using a replenisher as described in JP-A-54-62004. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246. Further, the above-described plate making process is preferably performed by an automatic developing machine as described in JP-A-2-7054 and JP-A-2-32357.

When the photosensitive lithographic printing plate using the photosensitive composition of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are erased,
It is preferable to use an erasing liquid as described in Japanese Patent Publication No. 2-13293. Further, as a desensitized gum applied as desired in the final step of the plate making process, Japanese Patent Publication No. Sho 62-168
No. 34, No. 62-25118, No. 63-52600, JP-A-62-7595
And those described in JP-A-62-11693 and JP-A-62-83194 are preferred. Furthermore, when the photosensitive lithographic printing plate using the photosensitive composition of the present invention is image-exposed, developed, rinsed or rinsed, optionally erased, and washed with water before burning, before burning. Nikko Sho 61
-2518, 55-28062, JP-A-62-31859, 61-1596
It is preferable to carry out treatment with a surface-regulating liquid as described in each publication of No. 55.

[0070]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the scope of the present invention. [Synthesis Example 1] 500 m equipped with a stirrer, a cooling pipe, and a dropping funnel
l In a three-necked flask, add N- (p-toluenesulfonyl)
7.18 g (0.030 mole) of methacrylamide, 5.94 g (0.025 mole) of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2.1 acrylonitrile
2 g (0.040 mole), benzyl acrylate 0.81 g (0.005 m
ole) and 30 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. 0.25 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred for 30 minutes under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further treated with N- (p-toluenesulfonyl) methacrylamide 2
8.72 g, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride 23.76 g, acrylonitrile 8.48 g, benzyl acrylate 3.24 g, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.00 g and N, N-dimethylacetamide 120 g Was dropped by a dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 65 ° C for 4 hours. After completion of the reaction, 100 g of methanol was added and the mixture was cooled, poured into 2 L of water with stirring, stirred for 30 minutes, and then filtered and dried to obtain 65 g of a white solid. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography and found to be 52,000. (Polymer compound (a) of the present invention)

[Synthesis Examples 2 to 6]
(B) to (f) were synthesized.

[0072]

[Table 1]

[Examples 1 to 9 and Comparative Examples 1 to 3] Thickness 0.24
mm JIS A 1050 aluminum plate
While supplying the suspension of miston and water to the aluminum surface
Brush brush with the following rotating nylon brush
Inning process was performed. The first brush has a hair length of 100 mm and a hair diameter of 0.95 m
m, flocking density 70 / cm^Two The second brush has a hair length of 80 mm,
Hair diameter 0.295mm, flocking density 670 / cm^Two Met. Brasserie
The rotation of each tool was 250 rpm. Brush grini
After washing well with water, 10% sodium hydroxide
Immerse in an aqueous solution at 60 ° C for 25 seconds to etch,
After washing with water, neutralization washing with 20% nitric acid and washing with water were performed. these,
Using a sine wave alternating current under the condition of VA = 12.7V
And 160 coulomb / dm in 1% nitric acid aqueous solution^TwoThe anode when electricity
The electrolytic surface roughening treatment was performed by the amount. The surface roughness was measured
However, it was 0.79 μ (Ra display). Followed by 1
30% for 30 seconds in 40% aqueous sodium hydroxide solution
Immersion in sulfuric acid aqueous solution at 60 ° C for 40 seconds
After that, in 20% sulfuric acid aqueous solution, current density 2A / dm^TwoAt
1.6g / m ^TwoAnodic oxidation with direct current to achieve the weight of the oxide film
Then, the substrate was adjusted. Surface of substrate treated in this way
Apply undercoat liquid (A) with the following composition and dry at 80 ° C for 30 seconds
did. 10mg / m coating amount after drying^TwoMet.

[Undercoat solution (A)] Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g Triethanolamine 0.05 g β-alanine 0.10 g Methanol 40 g Pure water 60 g Thus, the substrate (I) was prepared. Next, the following photosensitive solution was applied on this substrate (I) by rod coating for 12 m.
1 / m ^{2 was applied and} dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 1.15 g / m ² .
In order to further reduce the vacuum adhesion time, use JP-B-61-2898
A mat layer was formed as described in Japanese Patent Laid-Open Publication No. 6 (1996).

[Photosensitive solution] 0.8 g of an esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) Polymer compound of the invention (or comparative polymer compound) 0.4 g Cresol-formaldehyde novolak resin (meta / para ratio; 6: 4, weight average molecular weight 8,000) 1.5 g Phenol-formaldehyde novolak resin (weight average molecular weight 15,000) 0.2 g p -Normal octylphenol-formaldehyde resin described in U.S. Pat. No. 4,123,279) 0.02 g Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g 4- [pN, N-bis (ethoxycarbonylmethyl) aminophen ] -2,6-bis (trichloromethyl) -S-triazine (hereinafter abbreviated as triazine A) 0.07 g The counter anion of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) is converted to 1-naphthalenesulfonic acid. Changed dye 0.045 g F176PF (fluorinated surfactant, manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g MEK / (1-methoxy-2-propanol) = 15 g / 10 g

Through a step wedge manufactured by Fuji Photo Film Co., Ltd. (density difference of each step is 0.15), a distance of 1 m and 3 k
After exposure for 1 minute with a metal halide lamp w, Fuji Photo Film Co., Ltd. PS processor 900U
At 30 ° C. for 12 seconds, the molar ratio of SiO ₂ / K ₂ O is 1.16, S
Development was carried out with an aqueous solution having an iO ₂ concentration of 1.4%.

The development latitude (development tolerance) was evaluated by using a solution in which the pH was increased or decreased by 0.2 with respect to the above-described developer, and the change in the number of solid steps due to the pH was determined.
The smaller this value is, the better the development latitude is. After printing and exposure, printing durability was checked by using a printing machine Sprint manufactured by Komori Printing Machine Co., Ltd. to determine whether printing was normal, and evaluated by the number of prints until normal printing was stopped. The greater the number of printed sheets, the better the printing durability. The stainability was evaluated by visually observing the stains on the printed matter, and those having no stain in the non-image area were indicated by ○, those severely stained by x, and the middle thereof by Δ. Ballpoint pen aptitude is
Marks were drawn on the sample with a register mark drawing machine, developed after 2 minutes, and the suitability of the ballpoint pen was evaluated based on how the photosensitive layer was affected by the ballpoint pen.も の indicates that the non-image portion was not affected at all, △ indicates that the non-image portion was partially affected, and x indicates that the non-image portion was affected and the support was exposed.

The coupling was subjected to the above-described exposure and development, and the redness of the halftone was visually judged.て indicates no reddish color, Δ indicates a slightly reddish color, and x indicates a markedly reddish color.
Sensitivity change with time is 35 ° C. after exposure under the above conditions in order to examine the sensitivity variation with time from exposure to development.
After developing for 16 hours under the condition of a humidity of 85%, development was performed, and the sensitivity was compared with that of a lithographic printing plate developed immediately after exposure. When the sensitivity hardly fluctuated, the result was indicated by ○, when the printed matter was largely changed and a normal printed matter was not obtained, and the middle was indicated by Δ.
Table 2 shows the results.

[0079]

[Table 2]

As is clear from Table 2, the lithographic printing plates (Examples 1 to 6) using the vinyl polymer-based polymer compound of the present invention all have printing durability, stain, development latitude, ballpoint pen suitability, Excellent results were shown in the ring and the change in sensitivity with time. On the other hand, a lithographic printing plate manufactured without using the vinyl polymer compound of the present invention (Comparative Examples 1 to 5)
3) was insufficient in printing durability (Comparative Example 3) or inferior in stain, development latitude, ballpoint pen suitability, and change in sensitivity over time (Comparative Examples 1 and 2).

According to the present invention, a photosensitive lithographic printing plate produced by using a photosensitive composition containing a specific polymer compound of the present invention can provide printing durability, stain, development latitude, suitability for a ballpoint pen, and a cup. A lithographic printing plate excellent in ring and change in sensitivity over time can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 222/40 C08F 222/40 C08K 5/28 C08K 5/28 G03F 7/00 503 G03F 7/00 503 7 / 033 7/033 H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA04 AA06 AA11 AA12 AA13 AA14 AB03 AB16 AC01 AD03 BE01 CB14 CB41 CB42 CB48 FA17 2H096 AA06 AA25 BA10 GA08 4J07 BC101 BC121 AB07P AB07Q AL08Q AM21P AM21Q AM43P BA03Q BA05P BA12P BA15P BA28P BA32Q BA34P BA55Q BA58P BA59P BA62Q BC43P BC43Q BC69Q BC79Q BC83Q CA04 CA05 JA37

Claims (1)

[Claims] 1. A photosensitive composition comprising a vinyl polymer-based polymer compound insoluble in water and soluble in an alkaline aqueous solution, and o-naphthoquinonediazide, wherein the vinyl polymer-based polymer compound is represented by the following (A): A photosensitive composition comprising a copolymer containing at least one monomer unit derived from the monomer compound represented by (B). (A) A monomer compound having an active imino group represented by the following general formula (I) or (II). Embedded image Wherein A represents a hydrogen atom, a halogen atom or an alkyl group. B represents a single bond, an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group.
X ¹ is Represents X ² is (Wherein, R ¹ represents an optionally substituted alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group). [Formula 4] (Where E and E ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group; F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group; X ³ and X ⁴ is each independently Represents (B) Monomer compounds having an onium group represented by the following general formulas (III), (IV) and (V). Embedded image (Wherein, J represents a single bond or a divalent linking group, K represents a single bond, an aromatic group or a substituted aromatic group, M represents a single bond or a divalent linking group, provided that J and K is not a single bond at the same time, Y ₁ represents an atom of Group V of the periodic table, and Y ₂
Represents an atom belonging to Group VI of the periodic table. And Z ^- represents a counter anion. R ² represents a hydrogen atom, an alkyl group or a halogen atom. R ³ , R ⁴ , R ⁵ , and R ⁷ each independently represent a hydrogen atom or an optionally substituted alkyl group, aromatic group, or aralkyl group, and R ⁶ represents an alkylidine group or Represents a substituted alkylidine, wherein R ³ and R ⁴ or R ⁶ and R ⁷ may be bonded to each other to form a ring; When K represents a substituted aromatic group, the substituent is represented by the formula (I
In (I), (III) and (IV), the following (ii), (iii)
And a group represented by the formulas (iv). When substituted by two or more substituents, each substituent may be the same or different. In the formulas (ii) to (iv), M, Y ₁ , Y ₂ ,
Z and each group of R ^{3 to} R ⁷ are as defined above. )