JPH0654382B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. More specifically, it relates to a photosensitive composition comprising a positive-working o-naphthoquinonediazide compound and a specific polymer soluble in alkaline water.

[Prior Art] A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolac type phenolic resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate and as a photoresist.

However, due to the nature of the novolac type phenolic resin used as the main component, the adhesion to the substrate 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 solved and there was a limit in application.

Various polymers have been investigated as binders in order to solve such problems. For example, Japanese Examined Japanese Patent Publication No. 52-410
The polyhydroxystyrene or the hydroxystyrene copolymer described in JP-A No. 50 has certainly improved the film forming property, but has the drawback of being inferior in abrasion resistance. Further, JP-A-51-34711 proposes to use a polymer having a structural unit of an acrylic acid derivative in the molecular structure as a binder, but such a polymer is said to have a narrow range of appropriate developing conditions. There was a problem.

[Problems to be solved by the invention]

Accordingly, it is an object of the present invention to provide a photosensitive composition which gives a lithographic printing plate having a wide range of suitable developing conditions and a large printing durability. Another object of the present invention is to provide a photosensitive composition having good adhesion to a substrate and giving a flexible film.

[Means for solving problems]

The above problems can be solved by selecting a specific polymer having an active methylene group from among many polymers and combining this with a positive-working photosensitive material.

That is, the present invention provides a polymer having an active methylene group, which is a water-insoluble or alkali-water-soluble polymer having a structural unit represented by the following general formula [I] or [II] in the molecular structure, and a positive type Provided is a photosensitive composition comprising a photosensitive compound or a photosensitive mixture which acts.

(In the formula, A represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms, and B is -NH-, a phenylene group, a substituted phenylene group, X is Y is -CN, represent -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 sandwiched between X and Y
₂ 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 and a substituted alkyl group, a substituted alkenyl group, a substituted aryl group, and R ₃ represents an alkyl group in which a part or all of hydrogen is replaced with a halogen atom. ) (In the formula, D represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms, E represents —COO—, —CONR ₄ — or a substituted or unsubstituted phenyl group, and F is a substituted or unsubstituted group. substituted alkylene group, a phenylene group or aralkylene group, G is _{-CONR 4 -, - NR 4 CONR} 4 -, - NR 4 C
_{OO -, - NR 4 CO -} , - OCONR 4 -, - NR 4 -, - COO -, - OCO -, - CO
_{-, - O-, SO 2 -} , - NR 4 SO 2 - or -SO ₂ NR ₄ - represents a. R ₄
Represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. When two or more R _4's are present in the same molecule, they may be the same or different. l, m and n represent 0 or 1. However, l, m, and n are not 0 at the same time. Q is represented by formula (III), R ₅ is an unsubstituted or substituted anilino group, an acylamino group,
Represents a ureido group, R ₆ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, R ₅ and R
Any part of ₆ is connected to G in the general formula [II]. ) In the compound represented by the above general formula [I] or [II], A is preferably a hydrogen atom or a methyl group, and B is A phenylene group is preferred, and In the case of, it is preferable that the carbonyl group is directly bonded to the carbon bonded to A. Further, as the substituted phenylene group, F,
A halogen atom such as Cl and Br, an alkyl group, an alkoxy group, a nitro group, and a phenylene group substituted with a cyano group are preferable. X is preferably And R ₁ is preferably —CH ₂ —CH ₂ —, —CH ₂ — or phenylene group. For Y, Is preferable, and as R ₂ , an alkyl group is preferable, and a methyl group is particularly preferable. -R ₃ is -CF ₃ , -CHF ₂ , -CF ₂ CF
₃ is preferred.

D in the general formula [II] is particularly preferably a hydrogen atom or a methyl group, and R ₆ in the general formula [III] is an alkyl group or a substituted alkyl group (for example, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.). ), An aryl group or a substituted aryl group [as a substituent, an alkyl group (eg, methyl group, ethyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenyloxy group, etc.), alkoxycarbonyl Group (eg methoxycarbonyl group), acylamino group (eg acetylamino group), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group etc.), dialkylcarbamoyl group (eg dimethylcarbamoyl group), arylcarba group Group (eg phenylcarbamoyl group), alkylsulfonyl group (eg methylsulfonyl group), arylsulfonyl group (eg phenylsulfonyl group), alkylsulfonamide group (eg methanesulfonamide group, arylsulfonamide group (eg phenylsulfonamide group) ), Sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group), alkylthio group (eg methylthio group, arylthio group (eg phenylthio group), cyano group , Nitro group, and halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more 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. ], A heterocyclic group (for example, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R ₁ and R _{2 of} the general formula [I], E, F and R of the general formula [II]
₄ , substituents for R ₅ include an alkyl group (eg, methyl group, ethyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenyloxy group, etc.), an alkoxycarbonyl group (eg, Methoxycarbonyl group, etc.), acylamino group (eg acetylamino group), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group etc.), dialkylcarbamoyl group (eg dimethylcarbamoyl group), arylcarbamoyl group (eg phenylcarbamoyl group) Group), alkylsulfonyl group (eg methylsulfonyl group), arylsulfonyl group (eg phenylsulfonyl group), alkylsulfonamide group (eg methanesulfonamide group), arylsulfonamido Group (eg phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group), alkylthio group (eg methylthio group, arylthio group ( Examples thereof include a phenylthio group), a cyano group, a nitro group, and a halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different.

As the water-insoluble and alkali-water-soluble polymer having the structural unit represented by the above general formula [I] or [II] in the molecular structure, PKa; 4 to 11, more preferably 5 to 9 active methylene groups are used. Polymers having in the molecular structure are preferred.
Further, a polymer having an active methylene group directly bonded to at least one or more groups selected from a carbonyl group and a sulfonyl group in the molecular structure is preferable.

As the above-mentioned polymer used in the present invention, those having a wide range of molecular weights can be used, but when measured by gel permeation chromatography using polystyrene as a standard, the weight average molecular weight is 500 to 1,000,
000 is preferable, and more preferably 4,000 to 30.
It is 10,000.

In the photosensitive composition of the present invention, the amount of the polymer having an active methylene group is 3 to 90% by weight, preferably 10 to
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 of only the structural unit of the general formula [1] or the general formula [II] or the general formula [I] and the general formula [I].
The copolymer of I] may be used, or a multi-component copolymer having a repeating structure in which one or more of commonly used vinyl monomers are combined may be used. In the case of such a multi-component copolymer, the content of the structural unit represented by the general formula [I] is preferably 10 mol% or more, more preferably 20 mol% or more. As the structural unit used in combination with the structural unit represented by the general formula [I] or [II], for example, ethylene unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isobutylene, for example, styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, iso-butyl p-methate, n-butyl acrylate, hexyl acrylate, octyl acrylate, 2-hydroxyethyl acrylate, acrylate 2
-Acrylic acid and its esters such as cyanoethyl, glycidyl acrylate, dimethylaminoethyl acrylate, etc., such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate. Hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate,
2-hydroxyethyl methacrylate, 2-methacrylic acid
Methacrylic acid and its esters such as hydroxypropyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, etc., such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate. Vinyl ester such as vinyl benzoate, styrene, o-chlorostyrene, p-chlorostyrene and other styrenes such as acrylic acid, methyl acrylate, ethyl acrylate, acrylics such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl ethers such as cyclohexyl vinyl ether, acrylonitrile, methacrylonitrile, eg acrylamide, N Methyl acrylamide, N, N-
Acrylamides such as dimethyl acrylamide, N-tert-butyl acrylamide, N-octyl acrylamide and diacetone acrylamide, for example N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. And a structure shown by cleaving the unsaturated double bond of the vinyl-based monomer.

Other examples include substituted styrenes having a phenolic hydroxyl group disclosed in JP-A-58-203433.

Typical specific examples of the polymer having an active methylene group used in the present invention are shown below. In the following exemplified compounds, x, y and z represent mol% of each structural unit.

In the present invention, as the positive-working photosensitive compound used in combination with the above-mentioned polymer having an active methylene group, an o-naphthoquinonediazide compound is preferable, and JP-B-43-28.
Most preferred are the esters of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent No. 403. Other suitable orthoquinone diazide compounds include 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in U.S. Pat. Nos. 3,046,120 and 3,188,210. There is an ester with. Other useful o-naphthoquinonediazide compounds have been reported and known in numerous patents. For example, JP-A-47-5303
Issue, Dosho 48-63802, Dosho 48-63803
No. 48-96575 and 49-38701
No. 48-135354, Japanese Patent Publication No. 41-11222
No. 45-9610, No. 49-17481, and U.S. Pat. Nos. 2,797,213 and 3,45.
No. 4,400, No. 3,544,323, No. 3,5
73, 917, 3, 674, 495, and 3,
785,825, British Patent No. 1,227,602,
No. 1,251,345, No.1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890 and the like can be mentioned.

In addition to the o-naphthoquinonediazide compound, as a photosensitive compound or a photosensitive mixture which acts in a positive type, for example, a polymer compound having an orthonitrocarbinol ester group described in Japanese Patent Publication No. 56-2696 is also included in the present invention. Can be used for

Further, a mixture of a compound capable of generating an acid by photolysis and a compound having a C—O—C group or a C—O—Si group which is dissociated by an acid can be used in the present invention. Examples of such a mixture include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-89003), an orthoester or an amide acetal compound (special Kaisho 51-12
No. 0714), in combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429).
No.) and an enol ether compound (JP-A-55)
No. 12995), a combination with an N-acyliminocarbonic acid compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain (JP-A-56-56).
17345), a combination with a silyl ester compound (JP-A-60-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-1).
21446) and the like.

In the photosensitive composition of the present invention, the amount of the photosensitive compound or photosensitive mixture acting on these positive types is 10 to 50% by weight,
It is preferably 20 to 40% by weight.

In the composition of the present invention, in addition to the above polymers, known alkali-soluble polymer compounds such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. should be contained. You can The alkali-soluble polymer compound is preferably used in an amount of 70% by weight or less based on the total composition.

In the composition of the present invention, a cyclic acid anhydride may be added to enhance the sensitivity, a print-out agent for obtaining a visible image immediately after exposure, a dye or other filler as an image colorant may be added. As the cyclic acid anhydride, US Pat. No. 4,115,
Phthalic anhydride, as described in No. 128,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride,
Chloromaleic anhydride, α-phenylmaleic anhydride,
Examples include succinic anhydride and pyromellitic acid. By containing 1 to 15% by weight of these cyclic acid anhydrides in the total composition, the sensitivity can be increased up to about 3 times.
As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically, JP-A-50-36209 and JP-A-53-8
No. 128, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, JP-A-53-36223, and JP-A-54-7.
A combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728 can be mentioned. In addition to the salt-forming organic dyes described above, other dyes can be used as the image colorant. 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 # 60.
3, oil black BY, oil black BS, oil black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI42555),
Methyl violet (CI 42535), Rhodamine B
(CI45170B), Malachite Green (CI42
000), methylene blue (CI52015) and the like.

The composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here,
There are 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, ethyl acetate, etc. Solvents may be used alone or as a mixture. The concentration (solid content) in the above components is 2 to 50% by weight. Further, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, the solid content is generally 0.5 to 3.0 g /
m ² is preferred. Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

In the case of producing a lithographic printing plate using the photosensitive composition of the present invention, the support thereof may be a hydrophilized aluminum plate, for example, a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. There is a coated aluminum plate, and other zinc plate, stainless plate, chrome-treated steel plate, hydrophilized plastic film or paper can be used.

The developer for the photosensitive composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, tribasic ammonium phosphate, Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable and their concentration is 0.1-10% by weight,
Preferably, it is added in an amount of 0.5 to 5% by weight.

If necessary, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution.

〔The invention's effect〕

When a polymer having an active methylene group and a photosensitive compound and / or a photosensitive composition which act positively according to the present invention are combined, the adhesion to a substrate is good, the abrasion resistance is excellent, and the range of appropriate developing conditions is satisfied. Is wide (developing tolerance is wide)
A photosensitive composition can be obtained.

Next, the present invention will be described in more detail with reference to examples. All percentages in the following examples are% by weight unless otherwise specified.

[Reference example]

Polymer A1 having an active methylene group shown in the text
A synthetic example of A3 and A6 is shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound A1) Synthesis of Monomer 120 g of diketene and 150 ml of ethyl acetate were placed in a flask and cooled with ice, and hydroxyethyl methacrylate 1 was added thereto.
30 g, triethylamine 1.4 ml, hydroquinone 2.
After a mixture of 0 g and 50 ml of ethyl acetate was added dropwise over about 15 minutes, the mixture was gradually heated to react at 75-80 ° C for 1 hour. The reaction product was washed with 300 ml of water three times and then dried over magnesium sulfate. After distilling off the solvent with a rotary evaporator, the product was purified by distillation under reduced pressure (boiling point 7
0-75 ° C./0.5 mmHg) Acetoacetoxyethyl methacrylate (hereinafter abbreviated as AAEMA) 85.6b was obtained (yield 40%).

Polymerization AAEMA 16.07 g (0.075 mol) and methyl ethyl ketone 30.5 g were placed in a flask at 60 ° C.
The polymerization initiator V-65 [2,2′-azobis- (2,
4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries] 0.10
0 g was added and stirred. Two hours later, V-650.
After adding 100 g and stirring for a total of 4 hours, the content was n-
It was poured into hexane 1.5, and the produced solid was filtered off.
After drying under reduced pressure, 13.7 g of a polymer of Exemplified Compound A1 was obtained (yield 85%, weight average molecular weight 42,000).

Synthesis Example 2 (Synthesis of Exemplified Compound A3) Polymerization 21.4 g of AAAEMA obtained in Synthesis Example 1 and 5.0 g of ethyl acrylate were dissolved in 77 ml of methyl ethyl ketone,
In the same manner as in Synthesis Example 1, 0.14 g of V-65 was added twice and the mixture was stirred at 60 ° C. for a total of 4 hours for reaction. Next, 17.0 g of a polymer of Exemplified Compound A3 was obtained by the same post-treatment as in Synthesis Example 1 (yield 86%; weight average molecular weight 21,
000).

Synthesis Example 3 (Synthesis of Exemplified Compound A6) Synthesis of Monomer Monochloroacetonitrile 18.9 in a three-necked flask containing 41.6 g (0.20 mol) of potassium styrenesulfinate and 200 ml of N, N-dimethylformamide.
g (0.25 mol) was added dropwise over 40 minutes so that the internal temperature was 30 to 40 ° C. Then, after stirring at room temperature for 3 hours, 20 g of sodium sulfonate was dissolved in ice water 4
It was poured into 00 ml. The pH was adjusted to 1 to 3 by adding 1N HC, and the precipitated solid was filtered off. This solid is ethanol 5
After heating to 00 ml to dissolve it, activated carbon was added and stirred, and then the activated carbon was removed by filtration. The filtrate was concentrated to obtain 10.8 g of the objective monomer 4 (cyanomethylsulfinyl) -styrene (yield 26%).

Polymerization 4- (cyanomethylsulfinyl) -styrene 20.7
In a flask similar to that used in Synthesis Example 1 containing 3 g (0.1 mol) and 69.1 g of ethyl acetate, V-65 was added twice by 0.14 g by the same method and stirred for a total of 4 hours to obtain Synthesis Example 1. Polymer 17 of Exemplified Compound A6 after similar post-treatment.
0 g was obtained (yield 82%; weight average molecular weight 23.0).
0).

The polymers of A2, A5, A7 and A8 were prepared according to Synthesis Example 1.

〔Example〕

Example 1 An aluminum plate having a thickness of 0.30 is nylon brushed 40
The surface was grained using a 0-mesh aqueous suspension of pumice and then thoroughly washed with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This is V
Electrolytic surface roughening treatment was performed in an aqueous 1% nitric acid solution under the condition of _A = 12.7 v in a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μ (Ra display). Subsequently, it was immersed in a 30% H ₂ SO ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, then in a 20% H ₂ SO ₄ aqueous solution, the current density was 2 A / d.
thickness at m ² was anodized to be 2.7 g / ^{m 2.}

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

Naphthoquinone- (1,2) -diazido- (2) -5-sulfonyl chloride esterification reaction product of cresol novolac resin 0.75 g m-cresol novolac resin 1.40 g tetrahydrophthalic anhydride 0. 15 g Polymer shown in Table 1 0.70 g 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine 0.02 g Naphthoquinone-1,2-diazide-4-sulfonic acid chloride De 0.03 g Crystal violet 0.01 g Oil blue # 603 0.015 g (manufactured by Orient Chemical Industry Co., Ltd.) Ethylene dichloride 18 g 2-Methoxyethyl acetate 12 g The applied amount after drying was 2.1 g / m ² . Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a metal halide lamp of 2 KW. The exposed photosensitive lithographic printing plate was immersed in a 4% aqueous solution of sodium metasilicate for 1 minute to develop it, and then processed according to a conventional method to obtain a lithographic printing plate. The lithographic printing plate thus obtained was printed on an offset printing machine to test the printing durability. If the number of sheets with poor printing durability is small, the image area will be worn out and ink will not adhere, and normal printed matter cannot be obtained.

In addition, in order to examine the range of the range of appropriate development conditions (development acceptability), the change in tone reproducibility in the case of immersion in the developing solution for 5 minutes and development and immersion for 1 minute and development was examined. Those with almost no change are indicated with a circle, those with a large change are indicated with a cross, and the middle is indicated with a triangle. Further, in order to examine the adhesion and flexibility of the photosensitive composition to the substrate, a constant load was applied to the image area with a diamond stylus after exposure, and after development, printing was performed to examine the ease of scratching. Good for scratches ○, very easy for ×, middle △
Displayed in. These results are shown in Table 1. From Table 1, it is apparent 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 whiler and dried at 100 ° C. for 2 minutes.

Esterification product of naphthoquinone (1,2) -diazide- (2) -5-sulfonyl chloride and pyrogallol-acetone resin 0.90 g (also described in US Pat. No. 3,635,709, description Example 1). Exemplified Compound No. 1 Described in Table 2 Cresol novolac resin (ratio of m-cresol, p-cresol 5: 5) 2.1 g Amount obtained by subtracting the additive amount of the exemplified compound A1 in Table 2 2-trichloromethyl-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 8 g coating amount after drying 2.5 g / m ^The results of evaluation of these photosensitive lithographic printing plates in the same manner as in Example 1 are shown in Table 2. Table 2 shows that the photosensitive composition of the present invention has excellent performance. I understand.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-53-133429 (JP, A) JP-A-61-217034 (JP, A) JP-A-60-133440 (JP, A) JP-A-51- 34711 (JP, A)

Claims (3)

[Claims] 1. A polymer having an active methylene group, which has a structural unit represented by the following general formula [I] or [II] in the molecular structure and is insoluble in water or soluble in alkaline water, and acts on a positive type. A photosensitive composition containing a photosensitive compound or a photosensitive mixture as defined above. (In the formula, A represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms, and B is Represents a phenylene group or a substituted phenylene group, and X is Y is _{-CN -, - NO 2, -R} 3, represents the. 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 sandwiched between X and Y
₂ 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 and a substituted alkyl group, a substituted alkenyl group, a substituted aryl group, and R ₃ represents an alkyl group in which a part or all of hydrogen is replaced with a halogen atom. ) (In the formula, D represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms, E represents —COO—, —CONR ₄ — or a substituted or unsubstituted phenyl group, and F represents a substituted or unsubstituted group. represents an unsubstituted alkylene group, phenylene group or aralkylene group, G is _{-CONR 4 -, - NR 4 CONR} 4 -, - NR
_{4 COO -, - NR 4 CO} -, - OCONR 4 -, - NR 4 -, - COO -, - OCO -, - CO
-, - O -, - SO 2 -, - NR 4 SO 2 - or -SO ₂ NR ₄ - represents a. R
₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. When two or more R _4's are present in the same molecule, they may be the same or different. , M, n is 0
Or represents 1. However, m and n are not 0 at the same time. Q is represented by formula (III), R ₅ is an unsubstituted or substituted anilino group, an acylamino group,
Represents a ureido group, R ₆ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, R ₅ and R
Any part of ₆ is connected to G in the general formula [II]. ) 2. A polymer having an active methylene group is PK
a; The photosensitive composition according to claim (1), which has 4 to 11 active methylene groups in its molecular structure. 3. The polymer having an active methylene group has in its molecular structure an active methylene group directly bonded to at least one or more groups selected from a carbonyl group and a sulfonyl group. The photosensitive composition according to the item.