JP2002082435A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate developable with an aqueous alkali developing solution, having superior wear resistance, high wear resistance and superior chemical resistance, high plate durability even when printing with UV ink (ultraviolet-curing ink) is carried out without carryin out a burning processing and excellent in aging stability. SOLUTION: In the photosensitive planographic printing plate with a photosensitive layer containing a vinyl polymerized high molecular compound (A) insoluble in water and soluble in an alkaline aqueous solution and o-naphthoquinone diazide (B) on the substrate, the high molecular compound (A) is a copolymer containing at least one monomer of formula (I) (where X1, R1, R2, Y1, Z1, n and m are defined in this specification) and an acrylonitrile monomer as monomer units, and the amount of free acrylonitrile is <=1 part by mass based on 100 parts by mass of the total solid content of the high molecular compound (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate. More specifically, the present invention relates to a photosensitive lithographic printing plate having a photosensitive layer acting as a positive type, and having a photosensitive layer composed of a polymer compound having excellent abrasion resistance and chemical resistance, and having excellent stability 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, the novolak type phenol resin used as the main component has poor adhesion to the substrate due to its properties, the film is brittle, the coatability is poor, the abrasion resistance is poor, and the printing durability when used in lithographic printing plates Are not sufficient, and furthermore, the chemical resistance is poor, and especially when UV ink is used, the printing durability is extremely insufficient.

As a method for improving these various properties, a burning process (exposure, development, and heat treatment) is generally used. However, when the burning treatment is performed, there is a problem in that the low-molecular compound sublimates from the photosensitive layer in the image area and adheres to the non-image area, so that there is a problem that stains are easily generated during printing. In order to solve such a problem, various polymer compounds have been studied as binders. For example, the polyhydroxystyrene or hydroxystyrene copolymer described in JP-B-52-41050 certainly has improved coating properties, but has the drawback of inferior abrasion resistance and chemical resistance. Also, JP-A-51-347
No. 11 proposes to use as a binder a polymer compound having a structural unit of an acrylic acid derivative in a molecular structure. However, such a polymer compound has a narrow range of appropriate developing conditions and has a low wear resistance. There was a problem that the nature was not enough. In Japanese Patent Application Laid-Open No. 2-866, it is disclosed that a polymer compound having a sulfonamide group is used as a binder, as disclosed in JP-A-63-89864, JP-A-1-35436, and JP-A-1-52139. JP-A-8-339082 and the like have proposed using a polymer compound having an acrylic acid derivative having a phenolic hydroxyl group in its molecular structure as a binder. However, there is still a problem that the abrasion resistance is not sufficient, and the sensitivity is further reduced when the printing plate is stored over time.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate which can be developed with an aqueous alkaline developer, has excellent abrasion resistance, and has a high printing durability. UV resistance without burning process
It is an object of the present invention to provide a photosensitive lithographic printing plate having high printing durability even when printing using an ink (ultraviolet curable ink) and excellent in stability over time.

[0005]

As a result of various studies on the copolymer composition of the vinyl polymer, the present inventors have found that a vinyl copolymer obtained from a monomer mixture containing at least a monomer having an alkali-soluble group and an acrylonitrile monomer. The above object can be achieved by a photosensitive lithographic printing plate using, in a photosensitive layer, a photosensitive composition in which a polymer in which the amount of free acrylonitrile monomer in a copolymer is equal to or less than a predetermined amount is added to a photosensitive compound. And arrived at the present invention.

That is, the present invention provides a vinyl polymer type polymer compound (A) which is insoluble in water and soluble in an alkaline aqueous solution,
In a photosensitive lithographic printing plate having a photosensitive layer containing o-naphthoquinonediazide (B) on a support, the vinyl polymer type polymer compound (A) is represented by at least one kind of the following general formula (I). It is a copolymer containing a monomer and an acrylonitrile monomer as monomer units, and the free acrylonitrile monomer is 1 part by mass or less based on 100 parts by mass of the total solid content of the vinyl polymer compound (A). The photosensitive lithographic printing plate described above, which is a feature.

[0007]

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(Wherein, X ¹ represents —O— or —NR ³ —. R ¹ represents —H or —CH _3. R ² represents a single bond or a divalent organic group. Y ¹ Represents an arylene group, Z ¹ represents a group having an acidic hydrogen atom, n represents 0 or 1, and n is 1 when R ² is a single bond and when Z ¹ is —OH. m represents an integer of 1 or more, and R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the photosensitive composition used in the photosensitive layer of the photosensitive lithographic printing plate of the present invention will be described in detail. The vinyl polymer compound (A) used in the present invention, which is insoluble in water and soluble in an alkaline aqueous solution,
It is a polymer compound containing at least one compound represented by the general formula (I) and acrylonitrile as monomer units. This polymer compound can be obtained by polymerizing a monomer mixture containing these monomer units in a suitable solvent using a known polymerization initiator. The compounds having an alkali-soluble group represented by formula (I) are shown below.

[0010]

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(Wherein, X ¹ represents —O— or —NR ³ —; R ¹ represents —H or —CH ₃ ; R ² represents a single bond or a divalent organic group; Y ¹ Represents an arylene group, Z ¹ represents a group having an acidic hydrogen atom, n represents 0 or 1, and n is 1 when R ² is a single bond and when Z ¹ is —OH. m represents an integer of 1 or more, and R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

In the above formula, the group having an acidic hydrogen atom in Z ¹ includes —OH, —COOH, and —SO ₂ N
_{^{HR 4, -NHSO 2 R 5,}} CONHSO 2 R 6, -SO 2 N
_{^{HCOR 7, -NHCONHSO 2 R 8,}} -SO 2 NHCO
NHR ⁹ , —CONHSO ₂ NHR ¹⁰ , NHSO ₂ NHC
OR ¹¹ , -SO ₂ NHSO ₂ R ¹² , -COCH ₂ CO
R ^13, include _{^{-OCONHSO 2 R 14, SO 2 NHCOOR}} 15. R ⁴ , R ⁹ and R ¹⁰ represent a hydrogen atom or an optionally substituted alkyl, cycloalkyl, aryl or aralkyl group having 1 to 12 carbon atoms.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each may have a substituent, and may have 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group, and an aryl group. Alternatively, it represents an aralkyl group.

Among the compounds represented by the general formula (I), those particularly preferably used in the present invention are those wherein Y ¹ is a phenylene group or a naphthylene group, and Z ¹ is --OH or --COO.
H, -SO ₂ NHR ^4, a -NH ₂ SO ₂ R ^5, n is 1
In it, m is 1 or 2, X ¹ is -NR ³ - when the R ³ is a hydrogen atom, R ⁴ may have an alkyl group or substituent of a hydrogen atom, C _{1 ~ 3} A phenylene group,
R ⁵ is a alkyl group or a substituent of C _{1 ~ 3} is also a phenylene group. R ² is not particularly limited as long as it connects X ¹ to Y ¹ or Z ¹ when n is 0, but examples of the divalent organic group may have a substituent, for example. Examples include those containing an alkylene group, a cycloalkylene group, an arylene group, and further an ester linking group, an amide linking group, an imide linking group, an ether linking group, a urethane linking group, and a urea linking group. R ² particularly preferably used in the present invention is a single bond, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having a linking group. As a linking group, a urea group,
Examples include a urethane group, a sulfonamide group, an ester group, and an amide group.

Examples of the low molecular compound represented by the general formula (I) include, for example, JP-A-63-89864, JP-A-63-226641, JP-A-2-866,
JP-A-8-39082, Japanese Patent Application No. 11-49769.
And the compounds described in Japanese Patent Application Publication No. As such low molecular weight compounds, preferably, the following compounds (M1) to (M
20).

[0015]

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[0016]

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[0017]

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The content of the compound represented by the general formula (I) having an alkali-soluble group which can be suitably used as a monomer component of the vinyl polymer type polymer compound (A) which is insoluble in water and soluble in an alkaline aqueous solution is 3 ４０40 mol%. Preferably it is 10 to 35 mol%. If it is less than 3 mol%,
If the amount exceeds 40 mol%, it may cause development flow or deterioration of printing durability, which is not suitable.

Acrylonitrile, which is an essential component in the monomer mixture of the present invention, accounts for 40 mol% to 8 mol% of the copolymer component.
0 mol%, preferably 45 mol% to 75 mol%, more preferably 50 mol% to 65 mol%. 40 mol%
If it is less than 80, the printing durability when using UV ink is low,
If the amount exceeds mol%, it causes the development flow and is not suitable.

In the present invention, the residual amount of free acrylonitrile monomer in the vinyl polymerizable polymer compound (A) soluble in the water-insoluble alkaline aqueous solution is 100 parts by mass of the total solid content of the vinyl polymerizable polymer compound (A). If the amount exceeds 1 part by mass, the sensitivity is significantly reduced due to the storage of the printing plate over time, which is not suitable. The vinyl polymer type polymer compound (A) of the present invention is obtained by dissolving a monomer mixture containing a monomer having an alkali-soluble group represented by the general formula (I) and an acrylonitrile monomer in an appropriate organic solvent as described above. Can be obtained by polymerization using a radical polymerization initiator.In this case, if the charged amount of acrylonitrile monomer is large, unreacted acrylonitrile remains in the system, and the polymer solution is poured into a large amount of water or the like. Even if the generated precipitate is filtered, it is taken into the precipitate and it is difficult to completely remove the precipitate. In order to remove the remaining acrylonitrile monomer, it is necessary to repeat precipitation and precipitation in water, but the load of wastewater treatment is large and there are many problems in cost. On the other hand, polymerization is carried out in an organic solvent used as a coating solvent for the PS plate photosensitive layer, and after the reaction is completed, the remaining acrylonitrile monomer is azeotropically distilled off with the organic solvent under reduced pressure to give a polymer compound (A) having a small amount of free acrylonitrile monomer. Is preferred because

The monomer component for the water-insoluble and alkaline aqueous solution-soluble vinyl polymerizable polymer compound (A) according to the present invention includes, in addition to the monomer represented by the above general formula (I) and the acrylonitrile monomer, an amide group. Can be suitably used as a copolymerizable monomer. Examples of such copolymerized monomers include acrylamide, N-methylacrylamide, N
-Ethylacrylamide, Nn-propylacrylamide, N-iso-propylacrylamide, Nn-
Butylacrylamide, Nn-butylacrylamide, N-iso-butylacrylamide, N-sec-
Acrylamides such as butylacrylamide, N-tert-butylacrylamide, Nn-pentylacrylamide, Nn-hexylacrylamide, diacetoneacrylamide, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, Nn −
Propyl methacrylamide, N-iso-propyl methacrylamide, Nn-butyl methacrylamide, N-
n-butyl methacrylamide, N-iso-butyl methacrylamide, N-sec-butyl methacrylamide,
Examples include methacrylamides such as N-tert-butyl methacrylamide, Nn-pentyl methacrylamide, Nn-hexyl methacrylamide, and diacetone methacrylamide.

The content of the N-substituted (meth) acrylamide compound which may be suitably used as a monomer component of the vinyl polymer type polymer compound (A) which is insoluble in water and soluble in an alkaline aqueous solution is from 1 to 50. Mol%, preferably 5 to 30 mol%. If it is less than 1 mol%, it causes poor development or contamination, and if it exceeds 50 mol%, it causes a development flow and is unsuitable.

The vinyl polymer type polymer compound (A) used in the present invention comprises a compound having an alkali-soluble group represented by the general formula (I), acrylonitrile as an essential component, and one or more polymerizable compounds. It is preferable to copolymerize a monomer having a natural unsaturated bond, for example, a compound having a polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, styrenes and the like.

Specifically, for example, acrylates, for example, alkyl acrylates (the alkyl group preferably has 1 to 10 carbon atoms) (for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg, phenyl acrylate), methacrylic acid esters, such as alkyl methacrylate (carbon atom of the alkyl group) The number is preferably 1 to 10) (for example, methyl methacrylate, ethyl methacrylate, Tacrylate, 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 (for example, phenyl methacrylate) , Cresyl methacrylate, naphthyl methacrylate, etc.): styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, Benzylstyrene, chloromethylstyrene, trifluoro Methylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.),
Halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene,
Pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.).

Among these compounds having a polymerizable unsaturated bond, methacrylic esters, acrylic esters, methacrylic acid, acrylic acid, acrylic amides and methacrylamides are preferably used. . One or more of these can be used,
The suitably used content of these copolymer components is from 0 to 6
0 mol%, particularly preferably 10 to 50 mol%. Copolymers of one or more of these compounds having a polymerizable unsaturated bond, one or more of low molecular weight compounds represented by the general formula (I), and acrylonitrile include random, block, and graft forms. Any of them can be used.

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

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

Examples of the o-naphthoquinonediazide compound (B) used in the present invention include esters of 1,2-diazonaphthoquinonesulfonic acid chlorite and pyrogallol-acetone resin described in JP-B-43-28403. Is preferred. Other suitable orthoquinonediazide compounds include US Pat. No. 3,046,1.
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in JP-A-20 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported in many patents and are known.
For example, JP-A-47-5303 and JP-A-48-638
No. 02, No. 48-63803, No. 48-9657
No. 5, No. 49-38701, No. 48-13354
No., Japanese Patent Publication No. 37-18015, and No. 41-11222
Nos. 45-9610 and 49-17481, U.S. Pat. Nos. 2,797,213 and 3,454,4.
No. 00, No. 3,544,323, No. 3,573,91
No. 7, No. 3,674,495, No. 3,785,825
No. 1,227,602, UK Patent No. 1,251,3
No. 45, No. 1,267,005, No. 1,329,88
8, No. 1,330,932, German Patent No. 854,
890 and the like can be mentioned.

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.
No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
No. 2-178562, Japanese Patent Application No. 72-233292, U.S. Pat. Nos. 3,102,809 and 3,126,281.
No. 3,130,047 and No. 3,148,983
No. 3,184,310 and No. 3,188,210
No. 4,639,406 and the like, and those described in each gazette or specification.

When synthesizing these o-naphthoquinone cyanazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. Further, it is preferred to react in an amount of 0.3 to 1.0 equivalent. The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and amounts of introduction, but all the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.
It is. The amount of the o-naphthoquinonediazide compound in the photosensitive layer of the photosensitive lithographic printing plate of the present invention is 5 to 50% by mass.
And more preferably 15 to 40% by mass.

In the photosensitive layer of the photosensitive lithographic printing plate of the present invention, in addition to the polymer compound having an amide bond, a phenol formaldehyde resin, an m-cresol formaldehyde resin, a p-cresol formaldehyde resin,
-/ P- mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p- mixed), cresol formaldehyde resin such as mixed formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, poly A known alkali-soluble polymer compound such as halogenated hydroxystyrene can be contained. These alkali-soluble polymer compounds have a weight average molecular weight of 500 to 20,000.
Those having 0 and a number average molecular weight of 200 to 60,000 are preferred. Such an alkali-soluble polymer compound is used in an amount of 70% by mass or less of the total composition.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin, is used. It is preferable to use a condensate of phenol and formaldehyde in combination to improve the oil sensitivity of the image. In the photosensitive composition used in the photosensitive layer of the photosensitive lithographic printing plate according to the invention, it is preferable to add cyclic acid anhydrides, phenols and organic acids in order to increase the sensitivity. US Pat. No. 4,115,128 as a cyclic acid anhydride
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,3
6-endooxy- △ ⁴ -tetrahydrophthalic anhydride,
Examples include tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. As phenols, bisphenol A, p-nitrophenol, p-nitrophenol
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.

As the organic acids, JP-A-60-8894
No. 2, JP-A-2-96755 and the like. 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 Sulfuric acid, 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- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

In the photosensitive layer of the photosensitive lithographic printing plate of the present invention, Japanese Patent Application Laid-Open (JP-A) No. 62-251740 and Japanese Patent Application No. 2-1812 are disclosed in order to widen the development latitude.
Non-ionic surfactants as described in JP-A-48-48, JP-A-59-121044, Japanese Patent Application No. 2-1.
Amphoteric surfactants such as those described in 15992 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, manufactured by Dai-ichi Kogyo Co., Ltd., N-tetradecyl-N, N-betaine type), Alkyl-N-carboxyethyl-N
-Hydroxyethylimidazolinium betaine, Levon 15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkylimidazoline type) and the like. The nonionic surfactant,
The proportion of the amphoteric surfactant in the photosensitive composition is 0.0.
It is preferably from 5 to 15% by mass, more preferably from 0.1 to 5% by mass.
% By mass.

In the photosensitive layer of the photosensitive lithographic printing plate 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. Examples of the dye that can be used in the present invention include a cation having a basic dye skeleton described in JP-A-5-313359 and a sulfonic acid group as the only exchange group, and having 1 to 3 hydroxyl groups. A basic dye comprising a salt with an organic anion having 10 or more carbon atoms can be used. The addition amount is 0.2 to 5% by mass of the entire photosensitive composition. Further, compounds described in the above-mentioned JP-A-5-313359, which generate a photo-decomposed product which changes color tone by interacting with a dye, for example, JP-A-50-36209 (US Pat. No. 3,969,118) O-naphthoquinonediazide-4-sulfonic acid halogenide described in
No. 36223 (U.S. Pat. No. 4,160,671) describes trihalomethyl-2-pyrone and trihalomethyltriazine, and JP-A-55-62444 (U.S. Pat.
801), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat.
No. 982), for example, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds. These compounds can be used alone or as a mixture.

As a colorant for an image, the above-mentioned Japanese Patent Application Laid-Open No.
Other dyes besides the dyes described in JP 13359 can be used. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes.
Specifically, Oil Green BG, Oil Blue BO
S, Oil Blue # 603 (original manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B (C145170)
B), malachite green (C142000), methylene blue (C152015) and the like.

When the photosensitive lithographic printing plate of the present invention is produced, the support may be a hydrophilic aluminum plate, for example, a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrodeposited plate. There are aluminum plates, other zinc plates,
Stainless steel plates, chromed steel plates, plastic films and papers subjected to hydrophilic treatment can be used. Among these, an aluminum plate is preferable. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used,
For example, silicon, copper, manganese, magnesium, chromium,
An alloy of a metal such as zinc, lead, bismuth, and nickel and aluminum 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 is disclosed in U.S. Pat. No. 3,181,461. As described above, an aluminum plate that has been subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.
The anodizing treatment is, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current using an aluminum plate as an anode in an electrolyte solution of an inorganic acid such as boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of these salts alone or in combination of two or more. .

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilic treatments are used 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 to be done. Prior to graining the aluminum plate, the surface may be subjected to a pretreatment to remove rolling oil from the surface, if necessary, and to bring out 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 Japanese Patent Application Laid-Open No. 55-137993, Is preferred because of its strong adhesion to the support. The graining by the above-described method is preferably performed in a range where the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 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 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 one minute of immersion time at the setting of the working concentration and temperature. It can be higher or lower than this.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying an etching solution to the aluminum plate.
The treatment is preferably performed so as to be in the range of 10 to 10 g / m ² . As the etching agent, it is desirable 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 acid used for desmut treatment is
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. 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 thereof, the aluminum support An anodized film can be formed on the body surface.

The anodizing treatment conditions cannot be generally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by mass, and the liquid temperature is 5 to 70%.
° C, current density 0.5-60 amps / dm ² , voltage 1-10
0V and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, British Patent No. 1,4
US Patent No. 3,511,6 describes a method of anodizing at a high current density in sulfuric acid described in U.S. Pat.
The method of anodizing phosphoric acid as an electrolytic bath described in the specification of Japanese Patent No. 61 is preferable. The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilization treatment, if necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181. Alkali metal silicates such as those disclosed in U.S. Pat. No. 4,461,461 and potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. No. 4,153,461. There is a method of treating with polyvinyl phosphonic acid as described above.

Further, 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. An example of such a water-soluble compound is disclosed in
No. 7-16349. Combinations of water-soluble metal salts and hydrophilic cellulose (eg, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxylethyl cellulose, etc.), US Pat. No. 3,511,6
No. 61, polyvinylphosphonic acid disclosed in Japanese Patent Publication No. 46-35885, amino acids disclosed in Japanese Patent Application Laid-Open No. Sho 60-149491, and salts thereof (Na salt, K salt) Alkali metal salts, ammonium salts, hydrochlorides, oxalates, etc.
Acetates, phosphates and the like), amines having a hydroxyl group and salts thereof, and amines having a hydroxyl group and salts thereof disclosed in JP-A-60-232998 are particularly preferred.
The undercoat layer of such a water-soluble compound has a solid content of 1 mg /
It is preferable to provide in the range of m ^{2 to} 80 mg / m ² .

In the present invention, a photosensitive lithographic printing plate can be obtained by dissolving the components of each of the photosensitive compositions described above in a solvent capable of dissolving and coating the solution 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, dimethyl sulfoxide,
Dimethylacetamide, dimethylformamide, water, N
-Methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents are used alone or in combination. The concentration (solid content) in the above components is suitably from 2 to 50% by mass. The amount of coating varies depending on the application. For example, in the case of a photosensitive lithographic printing plate, the solid content is generally preferably from 0.5 to 3.0 g / m ² . The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate.

In the photosensitive layer of the photosensitive lithographic printing plate of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950. Agents can be added. The preferable addition amount is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass of the whole photosensitive composition. 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 close contact exposure using a vacuum furnace. Specifically, Japanese Patent Application Laid-Open Nos. 50-125805, 57-6582, and 6
Examples of the method include a method of providing a solid layer as described in each publication of 1-28986, and a method of thermally fusing a solid powder as described in Japanese Patent Publication No. 62-33737.

The developer for the photosensitive lithographic printing plate of the present invention is preferably an alkaline aqueous solution containing substantially no organic solvent, and specifically, sodium silicate, potassium silicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
An aqueous solution such as sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia, etc. They are suitably added so that their concentration is 0.1 to 10% by mass, preferably 0.5 to 5% by mass. Among these, potassium silicate, lithium silicate,
A developer containing an alkali silicate such as sodium silicate is preferable because it does not easily cause staining during printing, and the composition of the alkali silicate is [SiO ₂ ] / [M] = 0.5 to 0.5 in a molar ratio.
2.5 (where [SiO ₂ ] and [M] are SiO
The molarity of _{2 and} the molarity of the total alkali metal are shown. ), And the developer is preferably used which contains cut the SiO ₂ 0.8 to 8 wt%. 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 0.002 to 4% by mass, preferably 0.01.
１1% by mass.

In the developer, JP-A-50-5132 was used.
4, JP-A-59-84241 and JP-A-59-84241, and JP-A-59-75255, JP-A-60-111246 and JP-A-60-213943. JP-A-55-95946, by incorporating at least one nonionic surfactant as described in Japanese Patent Publications
As described in JP-A-56-142528, a polymer electrolyte is contained to enhance wettability to a photosensitive composition and development stability (development latitude). Are preferably used. The addition amount of such a surfactant is preferably 0.001 to 2% by mass, and 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 of the total alkali metal because less insoluble matter is generated in the developer, more preferably 90 mol% or more, and most preferably potassium is 100 mol% or more.
It is the case of mol%.

Further, the developing solution used in the present invention may contain a small amount of an organic solvent such as alcohol, or a solvent such as JP-A-58-190952.
Chelating agent described in Japanese Patent Publication No. 1-301
An antifoaming agent such as a metal salt or an organic silane compound described in JP-A-39 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.

The above-described photosensitive lithographic printing plate is disclosed in
-8002, 55-115045 and 59-58
Needless to say, the plate-making process may be performed by the method described in each publication of No. 431. That is, after the development processing, washing with water and then desensitization processing, or desensitization processing as it is,
Alternatively, treatment with an aqueous solution containing an acid or treatment with an aqueous solution containing an acid may be 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 power decreases, the processing power may be recovered by using a replenisher as described in JP-A-54-62004. In this case, U.S. Pat.
It is preferred to replenish by the method described in 882,246. Further, the plate making process as described above is disclosed in
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-2-32357.

When the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are to be erased, the method is described in JP-B-2-13293. It is preferable to use such an erasing liquid. Examples of the desensitized gum which is applied as required in the final step of the plate making process include JP-B-62-16834, JP-B-62-25118, JP-B-63-52600, and
Nos. 2-7595, 62-11693 and 62-83
What is described in each gazette of No. 194 is preferable. Furthermore, when the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, erasing if desired, and washing after washing with water, before burning, Japanese Patent Publication No. 61-2518 is used. And JP-A-55-28062, JP-A-62-31859, and JP-A-61-159655.

[0052]

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 N- (p-aminosulfonylphenyl) methacrylamide (3.60 g) was placed in a 200-ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
(0.015 mole), N-iso-propylacrylamide 1.13 g (0.01 mole), methyl methacrylate 1.50 g (0.015 mole), acrylonitrile 3.1
8 g (0.06 mole) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. To this mixture was added V-65 (2,2'-azobis (2,
4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd.)
0.25 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further charged with N- (p-aminosulfonylphenyl) methacrylamide (3.60 g) and N-i
1.13 g of so-propylacrylamide, 1.50 g of methyl methacrylate, 3.18 g of acrylonitrile, N,
20 g of N-dimethylacetamide and V-65 0.2
5 g of the mixture was added dropwise with a dropping funnel over 2 hours. After the addition, the mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 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 18 g.
g of a white solid [polymer compound (B-1)] was obtained. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography, and was 45,000. Further, when the free acrylonitrile content in the polymer compound was measured by gas chromatography, 1.5 parts by mass of acrylonitrile was detected in 100 parts by mass of the polymer. Further, this polymer compound (a-1) was redissolved in 60 g of methanol, and 3 L
And then stirred for 30 minutes and filtered and dried to obtain 17 g of a white solid [polymer compound (A-1)]. The free acrylonitrile content in this polymer compound was 0.1 part by mass per 100 parts by mass of the polymer.

[Synthesis Example 2] In a 200 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel, 2- (N '-(4
3.96 g (0.015 mole) of -hydroxyphenyl) ureido) ethyl methacrylate, 2.96 g of methyl methacrylate.
50 g (0.025 mole), acrylonitrile 3.18 g
(0.06 mole) and 20 g of methyl ethyl ketone, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. 0.25 g of V-601 (dimethyl 2,2'-azobisisobutyrate) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 73 ° C. To the reaction mixture was further added 3.96 g (0.015 mol) of 2- (N '-(4-hydroxyphenyl) ureido) ethyl methacrylate.
e), 2.50 g (0.025 mol) of methyl methacrylate
e), a mixture of 3.18 g (0.06 mole) of acrylonitrile, 20 g of methyl ethyl ketone, and 0.25 g of V-601 was dropped by a dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 73 ° C. for 2 hours. Polymer 10 in the obtained polymer compound solution [polymer compound (B-2)]
0 parts by mass contained 3.0 parts by mass of acrylonitrile free monomer. After completion of the reaction, 20 g of propylene glycol monomethyl ether was added, and the mixture was distilled under reduced pressure. Vacuum distillation is about 600 mmHg at an internal temperature of 70-80 ° C.
And concentrated under reduced pressure. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 61.0.
00. The content of free acrylonitrile in this polymer compound was measured by gas chromatography, and as a result, 0.4 part by mass of acrylonitrile was detected in 100 parts by mass of the polymer. The concentration was adjusted by adding methyl ethyl ketone to obtain a solution [polymer compound (A-2)] having a concentration of 30%.

[Synthesis Examples 3 to 7] Polymer compounds (A-3) to (A-7) shown in Table 1 in the same manner as in Synthesis Examples 1 and 2.
Was synthesized.

[0056]

[Table 1]

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "%" indicates "% by mass" unless otherwise specified.

[Examples 1 to 8 and Comparative Examples 1 to 4] An aluminum plate having a thickness of 0.30 mm was
The surface was grained with an aqueous suspension of mesh pumistone, and then thoroughly washed with water. After etching by dipping in a 10% sodium hydroxide solution at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This was converted to 160 coulombs / dm ^{2 in} a 1% nitric acid aqueous solution using a sine wave alternating current under the condition of VA = 12.7V.
The electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. When the surface roughness was measured, it was 0.6 μ (Ra). Then immersed in a 30% aqueous H ₂ SO ₄ solution at 55 ° C.
After desmutting for 20 minutes, the substrate was anodized in a 20% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ^{2 so} as to have a thickness of 2.7 g / m ² to prepare a substrate. The undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² .

Undercoat solution (A) Aminoethylphosphonic acid 0.01 g Phenylphosphonic acid 0.15 g Triethanolamine 0.05 g β-alanine 0.10 g Methanol 40 g Pure water 60 g The substrate (I) was thus prepared.

Next, the next photosensitive liquid is placed on the substrate (I).
(B), (C) by rod coating, 22ml / m^TwoPaint
And dry it at 100 ° C for 1 minute for positive photosensitive lithographic printing
Plates [B] -1 to [B] -8, [C] -1 to [C] -4
Obtained. Application amount after drying is about 1.5g / m ^TwoMet. Still feeling
Optical liquid [B] -1 to [B] -8, [C] -1 to [C] -4
Table 1 shows the present invention or comparative polymer compounds used for
Used.

[Photosensitive solution (B)] Esterified product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride (esterification ratio: 90 mol%) 0.45 g cresol-formaldehyde Novolak resin (meta-para ratio; 6 to 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% of unreacted cresol) 0.2 g m-cresol-formaldehyde novolak resin (weight average Molecular weight 1,700, number average molecular weight 600, 1% of unreacted cresol contained) 0.3 g condensation product of pyrogallol and acetone (weight average molecular weight 2,200, number average molecular weight 700) 0.1 g present invention 1.1 g (or solid content in terms of concentration in the case of a solution) of p-normal octylpheno -Formaldehyde resin (described in U.S. Pat. No. 4,123,279) 0.02 g naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0 0.01 g Benzoic acid 0.02 g 4- [p-N- (p-hydroxybenzoyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 0.02 g N- (1,2-naphthoquinone-2 -Diazido-4-sulfonyloxy) -cyclohexane-1,2-dicarboxylic acid imide 0.01 g Dye in which the counter anion of Victoria Pure Blue BOH (produced by Hodogaya Chemical Co., Ltd.) is changed to 1-naphthalenesulfonic acid. 05g Curcumin 0.005g 1- (α-methyl-α- (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl) -4- [α, α-bi S (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] benzene (compound (X) of JP-A-6-282067) 0.04 g Megafax F-176 (Dainippon Ink and Chemicals, Inc.) 0.01 g methyl ethyl ketone 10 g γ-butyrolactone 5 g 1-methoxy-2-propanol 5 g

[Photosensitive Solution (C)] Esterified product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride (esterification ratio: 90 mol%) 0.45 g of the present invention 1.7 g of high molecular compound (or comparative high molecular compound) (in the case of a solution, solid content in terms of concentration) naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0.02 g benzoic acid 0.02 g 4- [p-N- (p-hydroxybenzoyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 0.02 g N- (1,2-naphthoquinone-2-thiazide-4) -Sulfonyloxy) -cyclohexane-1,2-dicarboxylic acid imide 0.01 g of Victoria Pure Blue BOH [produced by Hodogaya Chemical Co., Ltd.] Dye with an anion changed to 1-naphthalenesulfonic acid 0.05 g Curcumin 0.005 g 1- [α-methyl-α- (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] -4- (α, α -Bis (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] benzene (compound (X) of JP-A-6-282067) 0.04 g Megafaq F-176 (Dainippon Ink Chemical Industry Co., Ltd.) Fluorinated surfactant) 0.01 g Methyl ethyl ketone 10 g γ-butyrolactone 5 g 1-methoxy-2-propanol 5 g

A line drawing and a positive transparent original of a halftone dot image were brought into close contact with the photosensitive layers of the photosensitive lithographic printing plates [B] -1 to [8] and [C] -1 to 4, and 70 cm with a 30-amp carbon arc lamp. Exposure was performed from a distance. The exposed photosensitive lithographic printing plates [B] -1 to 8 and [C] -1 to 4 were converted to DP-4.
The film was immersed and developed with an 8 diluted aqueous solution (trade name: manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. for 60 seconds.

The final number of printed sheets of the obtained planographic printing plates [B] -1 to [B] -8 and [C] -1 to 4 were examined. Also, the obtained lithographic printing plate [B]
-1 to 8 and [C] -1 to 4 at a temperature of 35 ° C and a humidity of 85%
Table 2 shows the sensitivity variation after 24 hours of constant temperature and humidity
It was shown to. Note that the sensitivity fluctuation was measured when the lithographic printing plate before and after storage was exposed through a step wedge manufactured by Fuji Photo Film Co., Ltd. (the density difference between each step was 0.15) and the change in the number of clear steps was less than 1 step. ○: One or more stages were evaluated as x.

As can be seen from Table 2, planographic printing plates [B] -1 to 6 and [C] -1 to 1 using the polymer compound of the present invention.
2 (Examples 1 to 8) were [B] -7, 8, [C] -3,
Compared with Comparative Example No. 4 (Comparative Examples 1 to 4), the number of printed sheets of the UV ink was large, the printing durability was very excellent, and the temperature fluctuation under constant temperature and constant humidity was small and excellent.

[0066]

[Table 2]

[0067]

As described above, the photosensitive lithographic printing plate of the present invention has a specific structure in which the amount of free acrylonitrile monomer in the polymer is not more than a predetermined amount in the photosensitive layer. By containing a copolymer comprising a monomer component, the photosensitive layer has good adhesion to a substrate,
Gives a flexible coating, and the resulting relief image has good abrasion resistance, good adhesion to the support, excellent chemical resistance, and is good even when printing with UV ink without burning treatment Thus, a lithographic printing plate having excellent printing durability can be provided. At the same time, there is an effect that a lithographic printing plate excellent in stability without a change in sensitivity even with storage time can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08F 220/44 (C08F 220/44 220: 12) 220: 12) (C08F 220/48 (C08F 220/48 220: 56) 220: 56) F-term (Reference) 2H025 AA12 AB03 AC01 AD03 BE01 CB06 CB14 CB15 FA17 2H096 AA06 BA10 GA08 4J100 AL08Q AM02P AM21Q BA03Q BA15Q BA16Q BA34Q BA37Q BA38Q BA58Q BA59Q BC43Q CA04

Claims (2)

[Claims] 1. A photosensitive lithographic printing plate having, on a support, a photosensitive layer containing a vinyl polymer type polymer compound (A) insoluble in water and soluble in an alkaline aqueous solution, and o-naphthoquinonediazide (B). The vinyl polymer type polymer compound (A) is a copolymer containing at least one monomer represented by the following general formula (I) and an acrylonitrile monomer as a monomer unit, and free acrylonitrile monomer is The above photosensitive lithographic printing plate, wherein the amount is 1 part by mass or less based on 100 parts by mass of the total solid content of the polymer compound (A). Embedded image (Wherein, X ¹ represents —O— or —NR ³ —. R ¹ represents —H or —CH _3. R ² represents a single bond or a divalent organic group. Y ¹ represents arylene Z ¹ represents a group having an acidic hydrogen atom, n represents 0 or 1, and R 1
^{When 2} is a single bond and Z ¹ is —OH, n is 1. m represents an integer of 1 or more. R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. ) 2. The content of the monomer unit derived from the general formula (I) is 3 to the vinyl polymer type polymer compound (A).
2. The photosensitive lithographic printing plate according to claim 1, wherein the content of the monomer unit derived from the acrylonitrile monomer is 40 to 80 mol%.