JPS63127237A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To realize the title composition capable of giving lithographic plate having large plate wear and having broad reasonable processing condition by selecting a polymer having an active methylene group from a large number of the polymers, and by combining the selected polymer with a photosensitive material which acts to positive type. CONSTITUTION:The titled composition comprises the polymer having the active methylene group and the sensitive compd. which acts to the positive type or its mixture. The polymer having the active methylene group is not specified in case that said polymer contains the active methylene group, but, is preferably the polymer which has PKa of 4-11, and further preferably, has the methylene groups of 5-9 in a molecular structure and preferably, is insoluble to water and is soluble to an alkaline aqueous solution. The polymer is preferably the polymer having the active methylene group which directly bonds to at least >=1 groups selected from a carbonyl or a sulfonyl group in the molecular structure, and is insoluble to water and is soluble to the aqueous alkaline solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits and photomasks.

More specifically, the present invention relates to a photosensitive composition comprising a positive-acting 0-naphthoquinonediazide compound and a specific alkaline water-soluble polymer.

[Conventional technology]

A photosensitive composition composed of an 0-naphthoquinone diazide compound and a novolak type phenol resin has been used industrially as an extremely excellent photosensitive composition in the production of lithographic printing plates and as a photoresist.

However, due to the nature of the novolak type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor abrasion resistance, and insufficient printing durability when used in lithographic printing plates. There were some drawbacks and limitations in terms of application.

In order to solve this problem, various polymers have been investigated as binders. For example, Tokuko Sho 52-410
Although the polyIJ' loquinstyrene or hydroxystyrene copolymer described in Japanese Patent No. 50 did have improved film properties, it had the drawback of poor abrasion resistance.

Furthermore, in JP-A-51-34711, it is proposed to use a polymer having a structural unit of an acrylic acid derivative in its molecular structure as a binder, but it is said that such a polymer has a narrow range of appropriate development conditions. There was a problem.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a photosensitive composition that can be used in a wide range of appropriate development conditions and provides a lithographic printing plate with high printing durability. Another object of the present invention is to provide a photosensitive composition that has good adhesion to a substrate and provides a flexible film.

[Means for Solving the Problems] The above problems could be solved by selecting a polymer having an active methylene group from among many polymers and combining it with a photosensitive material that acts in a positive tone.

That is, the present invention provides a photosensitive composition containing a polymer having an active methylene group and a positively acting photosensitive compound or a photosensitive mixture.

As the polymer having an active methylene group used in the present invention, any polymer having an active methylene group in the molecule can be used. have in the structure,
Moreover, those which are insoluble in water and soluble in alkaline water are preferred.

That is, since the polymer used in the present invention has an active methylene group in its molecular structure, it is characterized by dissociation in a developing solution, which is alkaline water. This is because performance can be obtained.

The above polymer preferably has an active methylene group directly bonded to at least one group selected from carbonyl groups and sulfonyl groups in its molecular structure, and is water-insoluble and alkaline water-soluble; , a polymer represented by the following general formula [■] or CI [] is preferred.

(In the formula, A represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and -NH-, a phenylene group, a substituted phenylene group, and -C
N, -NO□, -R3. Further, mSn represents 0 or 1, but it cannot be 0 at the same time.

R+ represents an alkylene group, a phenylene L-substituted fullkylene group, or a substituted phenylene group, and CH2 sandwiched between X and Y is directly bonded to the carbonyl group or sulfonyl group of X or B.

R2 represents an alkyl group, an alkenyl group, an aryl group, a substituted alkyl group, a substituted alkenyl group, or a substituted aryl group, and R3 represents an alkyl group in which part or all of the hydrogen atoms are substituted with halogen atoms. ) (wherein, D represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and E represents -COO-1-CO
NR4- or a substituted or unsubstituted phenyl group, F represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, G is -CONR1
-, -NR,C0NR4-1~NR1C0D-1-NR
,CO-,-Ol:ONRji,-NR,-,-C[]0
-, -0CO-, -CO-1-〇-1-302-, -N
R4SO□- or -SO□NR,-. R4 represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. When there are two or more R1s in the same molecule, they may be the same or different.

flSm,n represents 0 or 1. However, 11m,
n is never 0 at the same time. Q is the formula % formula % R5 is an unsubstituted or substituted anilino group, an acylamino group,
represents a ureido group, R6 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, Rs S
Any part of Re is connected to G in the general formula [1]. ) In the compound represented by the above general formula (1) or (II), it is preferable that A is a hydrogen atom or a methyl group is directly bonded to the carbon to which the carbonyl group is bonded to A. or,
Substituted phenylene groups include F, Cj! Preferred are phenylene groups substituted with halogen atoms such as SDr, alkyl groups, alkoxy groups, nitro groups, and cyano groups. X
is preferably -C)12-CH2-, -CH2-,
A phenylene group is preferred.

An alkyl group is preferable, and a methyl group is particularly preferable. -R8 is -CF3, -CtlF2, -CF2C
Fa is preferred.

D in the general formula [II] is particularly preferably a hydrogen atom or a methyl group, and R6 in the general formula t"III) is an alkyl group, a substituted alkyl group (for example, haloalkyl such as fluoroalkyl, cyanoalkynohebenzylalkyl, etc.). ), aryl group or substituted aryl group [
Examples of substituents include alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenyloxy group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, etc.), Acylamide 7 group (e.g. acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, etc.)
, dialkylcarbamoyl group (e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide) group), arylsulfonamide group (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio group (e.g. Methylthio group, arylthio group (e.g. phenylthio group),
Examples include a cyano group, a nitro group, and a halogen atom (for example, fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ], heterocyclic groups (eg triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R1, R2-1 of general formula [I], El of general formula [II,]
Substituents for FSRa and Rs include alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenyloxy group, etc.), alkoxycarbonyl groups (e.g., methoxy group, etc.). carbonyl group, etc.), acylamino group (e.g. acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g. methylcarbamoyl group,
ethylcarbamoyl group), dialkylcarbamoyl group (e.g. dimethylcarbamoyl group), aryl cuff 1
/hamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group),
Alkylsulfonamide groups (e.g. methanesulfonamide group), arylsulfonamide groups (e.g. phenylsulfonamide group), sulfamoyl groups, alkylsulfamoyl groups (e.g. evaethylsulfamoyl group), dialkylsulfamoyl groups (e.g. dimethyl Sulfamoyl group), alkylthio group (e.g. methylthio group, arylthio group (e.g. phenylthio group), cyanide group, nitro group, halogen atom (e.g. fluorine, chlorine, bromine, etc.), and there are two or more of these substituents. The times may be the same or different.

The polymer used in the present invention can have a wide range of molecular weights, but the weight average molecular weight is 500 to i, ooo when measured by gel permeation chromatography using polystyrene as a standard.
ooo is preferable, more preferably 4.000 to 30
It is 0,000.

In the photosensitive composition of the present invention, the amount of the polymer having active methylene groups is 3 to 90% by weight, preferably 10 to 90% by weight.
It is 70% by weight, more preferably 15 to 50% by weight.

The polymer having an active methylene group used in the present invention is a polymer having a repeating structure consisting only of structural units of general formula CI) or general formula [II], or a polymer having a repeating structure of only structural units of general formula CI) or general formula [ID and general formula [
The copolymer II) may be used, but it may also be a multicomponent copolymer having a repeating structure in which one or more types of commonly used vinyl monomers are combined. In the case of such a multicomponent copolymer, 10 structural units represented by the general formula [■]
The content is preferably mol % or more, and more preferably 20 mol % or more. Structural units used in combination with the structural unit represented by the general formula [■] or [ID include, for example, ethylene, propylene, inbutylene, butadiene,
Ethylenically unsaturated olefins such as isobutylene, such as styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, 1so-butyl p-methate, n-butyl acrylate, hexyl acrylate, octyl acrylate, acrylic Acrylic acid and its esters such as 2-hydroxyethyl acrylate, 2-cyanethyl acrylate, glycidinope acrylate, dimethylaminoethyl acrylate, e.g. methacrylic acid, metinope methacrylate, etinope methacrylate, n-butyl methacrylate. , 1so-butyl methacrylate, tert-butyl methacrylate,
Hexyl methacrylate, 2-ethylhexyl methacrylate, urinope methacrylate, tridecyl methacrylate,
cyclohexyl methacrylate, benzyl methacrylate,
2-hydroxyethyl meccrylate, 2-methacrylate
Hydroxypropinope dimethylaminoethyl methacrylate, diethylaminoethinopione methacrylate, glycidinobe mecacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid and its esters such as allyl methacrylate, e.g. vinyl acetate, vinylpepropionate, butyric acid Vinyl esters such as vinyl benzoate, vinyl styrene, ○-chlorostyrene, and p-chlorostyrene, such as acrylic acid, methyl acrylate, ethyl acrylate, acrylics, such as methyl vinyl ether, ethyl vinyl ether, and vinyl esters such as vinyl benzoate. Butyl vinyl ether/lz.

Vinyl ethers such as β-chloroethyl vinyl ether and cyclohexyl vinyl ether, acrylonitrile, meccrylonitrile, such as acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetone acrylamide, etc. Acrylamides, such as N-vinyl compounds such as N-vinylpyrrole, N-vinyl indole, and N-vinylhyrrolidone, have a structure in which the unsaturated double bonds of vinyl monomers are cleaved. I can give what is shown.

In addition, substituted styrenes having a phenolic hydroxyl group as disclosed in JP-A-58-203433 can also be mentioned.

Typical specific examples of polymers having active methylene groups used in the present invention are shown below. In addition, in the following exemplified compounds,
Ny and 2 represent the mole % of the respective structural units.

X:y=26:74 X:'1=34:66 X:y=33:67 x:y:z÷24 near 1:5 x:y=72:28 x:y=69:31 Δ11 x: y280:20 In the present invention, as the positive-acting photosensitive compound to be used in combination with the polymer having an active methylene group, an 0-naphthoquinone diazide compound is preferable, and is disclosed in Japanese Patent Publication No. 43-28
Most preferred is the ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent No. 403. Other suitable orthoquinone diazide compounds include the 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins described in U.S. Pat. Nos. 3,046,120 and 3,188,210. There is an ester with. Other useful 0-naphthoquinone diazide compounds are known and reported in numerous patents. For example, JP-A No. 47-5303,
The same town No. 48-63802, the same town No. 48-63803, the same town No. 48-96575, the same town No. 49-38701, the same town No. 48-13354, the same town No. 41-11222, the same town No. 45-9610, the same town No. 49-17481, U.S. Patent No. 2,797.213, U.S. Patent No. 3,454,400
No. 3,544,323, No. 3,573,91
No. 7, No. 3.674.495, No. 3,785.8
No. 25, British Patent No. 1, 227.602, British Patent No. 1, 2
No. 51.345, No. 1.267.005, No. 1.
Examples include those described in German Patent No. 329.888, German Patent No. 1.330,932, and German Patent No. 854,890.

In addition to the O-naphthoquinone diazide compound, as a photosensitive compound or photosensitive mixture that acts in a positive manner, for example, a polymer compound having an orthonitrocarbinol ester group described in the specification of Japanese Patent Publication No. 56-2696 may also be used in the present invention. It can be used for.

Furthermore, a mixture of a compound that generates an acid upon photolysis and a compound having a C-0-C group or a C-0-3i group that dissociates with an acid can also be used in the present invention. Examples of such compounds include, for example, a combination of a compound that generates an acid by photolysis and an acetal or 0,N-acetal compound (JP-A-48-89003), a combination with an orthoester or an amide acecool compound, etc. JP-A-51-1
20714), a combination with a polymer having an acetal or kecoul group in the main chain (JP-A-53-133429), a combination with an enol ether compound (JP-A-55-1986)
12995), a combination with an N-acylimino carbonate compound (JP-A-55-1126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-1)
7345), combinations with silyl ester compounds (JP-A-60-10247) and combinations with silyl ether compounds (JP-A-60-37549, JP-A-60-12)
No. 1446).

In the photosensitive composition of the present invention, the amount of these positively acting photosensitive compounds or photosensitive mixtures is 10 to 50% by weight,
Preferably it is 20 to 40% by weight.

In addition to the above polymers, the composition of the present invention may contain known alkali-soluble polymer compounds such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. I can do it. Such an alkali-soluble polymer compound accounts for 7% of the total composition.
It is preferable to use the additive in an amount of 0% by weight or less.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As a cyclic acid anhydride, US Pat. No. 4.115.
128, phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid etc. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times. Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-81
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 28, JP-A-53-36223, and JP-A-54-7
Examples include the combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728. In addition to the above-mentioned salt-forming organic dyes, other dyes can also be used as image coloring agents. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green BG, oil blue BO3, oil blue #60.
3. Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (CI42555),
Methyl violet (CI42535), rhodamine B
(CI4517QB), malachite green (CI42
000), methylene blue (CI52015), etc.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
These include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, toluene, and ethyl acetate. Solvents may be used alone or in combination.

The concentration (solid content) of the above components is 2 to 50% by weight. Further, although the coating amount varies depending on the application, for example, for photosensitive planographic printing plates, it is generally preferable that the solid content is 0.5 to 3.0 g/rn'. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosensitive composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate plate. There are coated aluminum plates, low zinc plates, stainless steel plates, chrome-treated steel plates, hydrophilized plastic films and paper.

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, diphosphoric acid, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight,
It is preferably added in an amount of 0.5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required.

〔Effect of the invention〕

According to the present invention, when a polymer having an active methylene group is combined with a photosensitive compound and/or a photosensitive composition that acts positively, good adhesion to the substrate, excellent abrasion resistance, and a suitable range of developing conditions can be obtained. (wide development tolerance)
A photosensitive composition can be obtained.

Next, the present invention will be explained in more detail by giving Examples. All percentages in the examples below are by weight unless otherwise specified.

[Reference example]

Polymer Δ1 having active methylene groups as shown in the text,
Synthesis examples of A3 and A6 are shown below.

Synthesis Example 1 (Synthesis of Exemplary Compound A1) Synthesis of Monomers 120 g of diketene and 150 mβ of ethyl acetate were placed in a flask and cooled on ice, and hydroxyethyl methacrylate (methacrylate) was added to the flask.
A mixture of 1.4 ml of ethylamine, 2.0 g of hydroquinone, and 50 mβ of ethyl acetate was added dropwise over about 15 minutes, and the mixture was gradually heated and reacted at 75 to 80° C. for 1 hour. The reaction product was washed three times with 300 mβ water and then dried over magnesium sulfate. After removing the solvent using a rotary evaporation lake, the product is purified by vacuum distillation.
(Boiling point: 70-75°C/0.5 mmHg) 85.6 g of acetoacetoxyethyl methacrylate (hereinafter abbreviated as AAEMA) was obtained (yield: 40%).

In a flask containing 16.07 g (0,075 mol) of polymerized AAEMA and 30.5 g of methyl ethyl ketone,
At 60°C, polymerization initiator V-65 [2,2'-azobis-
(2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries)
0.100 g was added and stirred. After 2 hours, more V
After adding -650,100 g and stirring for a total of 4 hours, the contents were poured into 1.5β n-hexane, and the produced solid was filtered out. Polymer 13 of Exemplary Compound A1 was dried under reduced pressure.
．． 7 g (yield 85%, weight average molecular weight 42.0
00).

Synthesis Example 2 (Synthesis of Exemplified Compound A3) 21.4 g of AAEMA obtained in Polymerization Synthesis Example 1 and 5.0 g of ethyl acrylate were dissolved in 77 ml of methyl ethyl ketone, and 0.14 g of ■-65 was added in the same manner as in Synthesis Example 1. The mixture was added in two portions and stirred at 60° C. for a total of 4 hours to react. Next, the same post-treatment as in Synthesis Example 1 was carried out to obtain 17yOg of a polymer of Exemplary Compound A3 (yield: 86%; weight average molecular weight: 21,000).

Synthesis Example 3 (Synthesis of 6 to Exemplary Compound) Monomer Synthesis Potassium styrene sulfinate 41.6 g (0,20
In a three-day flask containing 200 mj2 of N,N-dimethylformamide, 1 mol of monochloroacetonitrile was added.
8.9 g (0.25 mol) was added dropwise over 40 minutes so that the internal temperature was 30 to 40°C. After stirring for 3 hours at room temperature, 20 g of sodium sulfonate was poured into 400 mf of ice water. Add INHCβ to pH 1
The precipitated solid was filtered out. This solid was heated and dissolved in 500 ml of ethanol, activated carbon was added and stirred, and then the activated carbon was removed by filtration. Concentrate the filtrate to obtain the target monomer 4(cyanomethylsulfinyl)-styrene 10.8 gt-f8 (yield 26%)
.

Polymerized 4-(cyanomethylsulfinyl)-styrene 20.7
In a flask similar to Synthesis Example 1 containing 3 g (0.1 mol) and 69.1 g of ethyl acetate, 0.14 g of ■-65 was added twice in the same manner as in Synthesis Example 1, and stirred for a total of 4 hours. Polymer 1 of Exemplary Compound A6 was subjected to the same post-treatment as in 1.
7.0 g was obtained (yield 82%; weight average molecular weight 23,
000).

Note that polymers A2, A5, A7, and A8 were prepared according to Synthesis Example 1.

〔Example〕

Example 1 An aluminum plate with a thickness of 0.30 was coated with nylon graphite 40
The surface was gritted using a water suspension of 0 mesh pumice stone, and then thoroughly washed with water.

After etching by immersing in IJum (10% hydroxide) at 70° C. for 60 seconds, washing with running water, neutralizing with 20% HNO3, and washing with water. This was conducted in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of V = 12.7V.
Electrolytic surface roughening treatment was performed using an anode special electricity amount of 0 coron/dm2. When the surface roughness was measured, it was found to be 0.6μ (R
a). Subsequently, it was immersed in a 30% H2SO4 aqueous solution and desmutted at 55°C for 2 minutes.
% H2SO4 aqueous solution at a current density of 2 A/dm2 to a thickness of 2.7 g/g.

The following photosensitive solution was applied onto the thus obtained aluminum support using a whiler and dried at 100° C. for 2 minutes.

Esterification reaction product of naphthoquinone-(1,2)-diazide-(2)-5-sulfonyl chloride and cresol novolac ivy resin 0.75 gm- Talesol novolac resin 1.40 g Tetrahydrophthalic anhydride 0.15 g Polymers listed in Table 1 0.70 g 2-(p-butoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine 0.02 g Naphthoquinone-1,2-diazibi-4-sulphosphoric acid chloride
0.03g crystal violet
0.01 g Oil Blue #603 0
．． 015 g (Orient Kagaku Kogyo Co., Ltd. % formula %) The coating weight after drying was 2.1 g/m'. The exposed photosensitive lithographic printing plate was immersed in a 4% sodium metasilicate aqueous solution for 1 minute to develop it, and then treated according to a conventional method to obtain a lithographic printing plate.The lithographic printing plate thus obtained was We tested the rigidity by printing on an offset printing machine.If the printing durability is poor, the image area will wear out after a small number of sheets, and the ink will no longer adhere to it, making it impossible to obtain a normal printed product.

In addition, in order to investigate the wide range of appropriate development conditions (development acceptability), changes in tone reproducibility were investigated when developing by immersing in the developer for 5 minutes and developing by immersing for 1 minute. ○ indicates that there was almost no change, × indicates that there was a large change, and ∆ indicates that there is a significant change. In addition, in order to examine the adhesion and flexibility of the photosensitive composition to the substrate, the image area was scratched after exposure by applying a constant load with a diamond needle, and after development, the composition was printed and the ease of scratching was examined. ○ for items that are hard to get scratched, 1 for items that are extremely easy to get scratched, △ for those in between.
It was displayed in These results are shown in Table 1, and it is clear from Table 1 that the photosensitive composition of the present invention has extremely excellent performance.

Example 2 The following photosensitive solution was applied onto a support prepared in the same manner as in Example 1 using a wheeler, and dried at 100° C. for 2 minutes.

Esterified product of naphthoquinone (1,2)-diazide-(2)-5-sulfonyl chloride and pyrogallol-acetone resin 0.90 g (described in Example 1 of U.S. Pat. No. 3,635,709) Exemplary compound Nα1 Cresol novolak resin (ratio of m-cresol, p-cresol 5:5) listed in Table 2 2.1 g minus the addition prefix of Exemplary compound A1 in Table 2 2-trichloro Methyl-5-(4-hydroxystyryl)-1゜3.4-oxadiazole 0.04 g Phthalic anhydride 0.20 g Oil-soluble dye (CI42595) 0.03 g Ethylene dichloride 15 g Methyl cellosolve
8g coating amount after drying is 2.5g/m'
Met. Table 2 shows the results of evaluating these photosensitive lithographic printing plates in the same manner as in Example 1.
It can be seen that the photosensitive composition of the present invention has excellent performance.

Procedural amendment Commissioner of the Patent Office Black 1) Mr. Akihiro "■l, Indication of the case 1985 Patent Application No. 274432 2, Title of the invention Photosensitive composition 3, Person making the amendment Relationship with the case Name of originator (520) Fuji Photo Film Co., Ltd. 4, Agent

Claims (4)

[Claims] (1) A photosensitive composition comprising a polymer having an active methylene group and a positively acting photosensitive compound or a photosensitive mixture. (2) The polymer having an active methylene group has a PKa;
The photosensitive composition according to claim 1, which is a water-insoluble but alkaline water-soluble polymer having from 11 to 11 active methylene groups in its molecular structure. (3) The polymer having an active methylene group has an active methylene group directly bonded to at least one group selected from a carbonyl group and a sulfonyl group in its molecular structure, and is water-insoluble and alkaline water-soluble. The photosensitive composition according to claim 1, which is a polymer of (4) The polymer having an active methylene group is a water-insoluble, alkaline water-soluble polymer having a structural unit represented by the following general formula [I] or [II] in its molecular structure. ) The photosensitive composition described in item 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (In the formula, A represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and B is a ▲mathematical formula, chemical formula, table, etc. There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -NH -, represents a phenylene group, a substituted phenylene group, , there are tables, etc. ▼, Y is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. Yes ▼, -CN, -
It represents NO_2, -R_3. Also, m and n represent 0 or 1, but they cannot be 0 at the same time. R_1 represents an alkylene group, a phenylene group, a substituted alkylene group, or a substituted phenylene group, and CH_2 sandwiched between X and Y is directly bonded to the carbonyl group or sulfonyl group of X or B. R_2 represents an alkyl group, an alkenyl group, an aryl group, a substituted alkyl group, a substituted alkenyl group, or a substituted aryl group, and R_3 represents an alkyl group in which part or all of the hydrogen atoms are substituted with a halogen atom. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, D represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and E represents -COO-, - C.O.
NR_4- or a substituted or unsubstituted phenyl group, F represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, G is -CONR
_4-, -NR_4CONR_4-, -NR_4COO
-, -NR_4CO-, -OCONR_4-, -NR_
4-, -COO-, -OCO-, -CO-, -O-, -
SO_2-, -NR_4SO_2- or -SO_2N
Represents R_4-. R_4 represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. R_
When there are two or more 4's in the same molecule, they may be the same or different. l, m, n represent 0 or 1. However, l, m, n
are never 0 at the same time. Q is expressed by formula (III), and there are ▲mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・(I
II) R_5 represents an unsubstituted or substituted anilino group, acylamino group, or ureido group; R_6 represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group;
5. Any part of R_6 is connected to G in the general formula [II]. )