JPS63214747A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. suitable for a planographic printing plate having superior resistance to treating chemicals, high sensitivity and a wide development latitude by incorporating a specified compd. and a polymer having units each having a phenolic OH group in the molecule. CONSTITUTION:This photosensitive compsn. contains a compd. having a structure represented by the formula (where each of R1 and R2 is H, halogen atom, alkyl, aryl, carboxyl or a salt thereof, R3 is H, halogen atom, alkyl aryl or aralkyl, Y is bivalent (substd.) arom. group, X is a bivalent org. group and n=0-5) and a polymer having units each having a phenolic OH group in the molecular structure. A photosensitive planographic printing plate using the photosensitive compsn. has superior resistance to treating chemicals, especially a plate cleaner and a detergent soln. used in printing with UV ink, a wide development latitude, superior over-developability and under-developability. The compsn. is especially suitable for a positive type photosensitive planographic printing plate.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive composition suitable for positive-working photosensitive lithographic printing plates, and more specifically, a photosensitive composition that has excellent processing chemical resistance, sensitivity, and development latitude. The present invention relates to a photosensitive composition suitable for positive-working photosensitive lithographic printing plates.

(Background of the Invention and Prior Art) A positive-working photosensitive lithographic printing plate generally has an ink-receptive photosensitive layer formed on a hydrophilic support, which becomes solubilized by exposure to light. When this photosensitive layer is subjected to imagewise exposure and development, the non-image areas are removed while leaving the image areas, thereby forming an image. In planographic printing, the difference in properties is utilized: the image area is lipophilic and the non-image area is hydrophilic.

Conventionally, positive-working photosensitive lithographic printing plates have poor resistance to various processing chemicals used during printing, such as isopropyl alcohol contained in fountain solution, ink, surface preparation liquid, plate cleaner, etc. As a result, there was a drawback that the stiffness resistance decreased. In Japanese Patent Publication No. 43-28403, O
- It is described that resistance to processing chemicals was improved by using a naphthoquinodiazide sulfonic acid ester as a photosensitive component. It showed some good chemical resistance against processing chemicals used in printing with conventional oil-based inks. However, in recent years, printing using UV-curable U■ inks has been increasing, and the inks and processing chemicals (washing oil, plate cleaners, etc.) used for this UV ink printing require the above-mentioned photosensitive ingredients. is still insufficiently resistant.

In general, the development of photosensitive lithographic printing plates using 0-quinonediazide compounds is usually carried out with an alkaline aqueous solution developer, but the developing ability of the developer is subject to fluctuations under various conditions, such as fatigue due to large-volume processing and air pollution. Deterioration due to oxidation reduces the developing ability, and the photosensitive layer in the non-image area of the printing plate may not be completely dissolved even after processing. On the other hand, due to excessive replenishment of the developer or an increase in the bath temperature due to a rise in temperature, the developing capacity may exceed the specified limit, and the image area of the printing plate may be eroded or the halftone dots may disappear. There are cases. For this reason, photosensitive lithographic printing plates can be used with developing solutions with reduced throughput, or even with developing solutions with increased throughput compared to the standard.
It is desirable to have a wide development latitude that exhibits developability similar to that when processed with a standard developer.

Japanese Patent Publication No. 50-24641 describes the use of a polymer compound containing a repeating structural unit of a condensate of 0-naphthoquinonediazide sulfonic acid chloride and an ink pot such as p-hydroxymethacrylanilide as a photosensitive component. There is. By using the photosensitive component, resistance to processing chemicals used in UV ink printing was improved to some extent. However, it has the drawbacks of low sensitivity and extremely narrow development latitude. In addition, the special public
Publication No. 28401 describes a photosensitive composition containing a polymer containing p-hydroxymethacrylanilide or the like in a repeating structural unit as a binder.

In addition, Tokusei Publication No. 51-34711@ describes a photosensitive composition containing a polymer containing 4-(methacryloyloxyacetyl)phenol or the like in a repeating structural unit as a binder. Use of these photosensitive compositions also improved resistance to processing chemicals used in UV ink printing. However, when a conventionally known 0-naphthoquinonediazide compound is used as a photosensitive component, it has a drawback that the development latitude is very narrow.

(Object of the Invention) Therefore, an object of the present invention is to provide a photosensitive composition suitable for a photosensitive lithographic printing plate, which has excellent processing chemical resistance, high sensitivity, and excellent development latitude.

(Structure of the Invention) The above object of the present invention is to (A) provide a compound having a structure represented by the following general formula [I] and the general formula [I] (wherein R1 and R2 are respectively a hydrogen atom, a halogen atom, represents an alkyl group, an aryl group, a carboxyl group, or a salt thereof, R3 is a hydrogen atom, a halogen atom,
represents an alkyl group or an aryl group, R4 is a hydrogen atom,
Represents an alkyl group, aryl group or aralkyl group, Y
represents a divalent aromatic group which may have a substituent, and X is 2
(Represents an organic group of ilj, and n represents an integer of O to 5.)
(B) A photosensitive composition containing a polymer having a unit having phenolic OHM in its molecular structure.

The present invention will be explained in detail below.

In the general formula [I] of the present invention, R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a salt thereof;
An alkyl group such as a methyl group or an ethyl group, or a carboxyl group or a salt thereof (ammonium salt and alkali metal salt) is preferable, and a hydrogen atom is more preferable.

R3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, a halogen atom such as bromine or chlorine, or an alkyl group such as a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group. be.

R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

Each group represented by R1 to R→ includes those having a substituent.

Y represents a divalent aromatic group which may have a substituent, preferably a phenylene group or a naphthylene group which may have a substituent, and the substituent is an alkyl group such as a methyl group or an ethyl group. A halogen atom such as bromine or chlorine, a carboxyl group or a salt thereof, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group, a sulfo group, a cyam L nitro group, an acyl group, and the like. More preferably, Y is an unsubstituted phenylene group or a naphthylene group having a methyl group.

X represents a divalent organic group, such as an alkylene group, an arylene group, an aralkylene group, -CO-1-NH8O2-1
-8O2NH-1 or any combination of these groups, etc., but an alkylene group is preferred.

0 represents an integer from 0 to 5, preferably 1.

Next, the structure represented by the general formula [I] of the present invention is (1)
CHs (2) CHs A compound having a structure represented by general formula [I] of the present invention (
There are various methods for synthesizing the compound (hereinafter referred to as the compound of the present invention). For example, α, β-unsaturated acid chlorides or α, β-unsaturated acid anhydrides are reacted with primary or secondary amines having a phenolic hydroxyl group using a basic catalyst as necessary. Finally, in place of the 0-naphthoquinonediazide sulfonyl group in the structure represented by the general formula [I], water I! After synthesizing a compound having a structure corresponding to the one into which the group has been introduced, the obtained compound is then oxidized in the presence of an alkali in an organic solvent miscible with water.
-By condensation reaction with naphthoquinonediazide sulfonyl chloride, 0 at the position of the phenolic hydroxyl group
-A compound of the present invention can be obtained by introducing a naphthoquinonediazide sulfonyl group.

The proportion of the compound of the present invention in the photosensitive composition is 5 to 5.
60% by weight is preferred, particularly preferably 10-50% by weight.

The polymer having a unit having phenolic OHI in the molecular structure of the present invention (hereinafter referred to as the polymer of the present invention) is
A polymer containing at least one structural unit of the following general formulas [I[1 to [V]] is preferred.

General formula [II] 1+CRs R6-CR7-)- C0NRa-+AkB-OH General formula [1 [[] % formula % General formula [rV] +CRs Rs -CRT-)- -0H General formula [V] H In the formula , R5 and R6 each represent a hydrogen atom, an alkyl group, or a carboxylic acid group, preferably a hydrogen atom. R7 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group.

R8 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably an aryl group. A represents an alkylene group that may have a substituent that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a phenylene group that may have a substituent. Represents a naphthylene group which may have a group or a substituent.

The polymer of the present invention preferably has a copolymer-type structure, and monomer units that can be used in combination with the structural unit represented by the general formula [nl-[V] include, for example, ethylene, propylene, Ethylenically unsaturated olefins such as isobutylene, butadiene, isoprene, etc., styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, etc., acrylic grains such as acrylic acid, methacrylic acid, etc., e.g. itaconic acid , unsaturated aliphatic dicarboxylic acids such as maleic acid and maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α - Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate;
For example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylonitrile, p-chloroacrylanilide, ■-
Anilides such as nitroacrylanilide and -monomethoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, etc. vinyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-
Methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene derivatives such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinyl N-vinyl compounds such as virolne, N-vinylpyrrolidone,
There are vinyl monomers such as

These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, those used in combination with the structural units represented by general formulas [II] to [V] include (meta)
Acrylic acids, esters of aliphatic monocarboxylic acids, and nitriles are preferable because they exhibit excellent overall performance. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like.

These monomers may be bound in the polymer of the present invention in either a block or random manner.

Representative examples of the polymer of the present invention will be given below. In addition, in the compounds illustrated below, lylw is *! 1 average molecular weight, 1v
ln is the number average molecular weight, s, 1. o, m and n are
Each represents the mol% of the structural unit.

(al 9B, 9H.

(Mw = 2800Q Mw/Mn = 7.8 m
: n = 40 : 60) (Mw=22000.
Mw/Mn = 6.9 m:n:1=30:4
0:30) (Mw=33000.Mw/Mn=31
m:n:1=20:35:45)d1 (Mw=33000. Mw/Mn=7 m: n:
1=38:60:2) OHm:n:1=20:40:
40) (i) (Mw=20000. Mw/Mn=15man :J
= 30:35:35) 1° Knee Earth The composition of the present invention may contain a known alkali-soluble polymer compound. Examples of novolak resins include phenol formaldehyde resins, cresol formaldehyde resins, and phenol-modified xylene resins, and such alkali-soluble polymer compounds are used in an amount of 70% by weight or less of the total composition.

When the present invention is supplied as a positive-working photosensitive lithographic printing plate, an exposure visible image imparting agent and a dye are generally added. As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

As a compound that generates an acid upon exposure to light, the following general formula [
A trihaloalkyl compound or a diazonium salt compound represented by VI] or [■] is preferably used.

General formula [Vrl (where ><a is a trihaloalkyl group having 1 to 3 carbon atoms, WItiN, 51Se, PSZ is O, N51S
e 5PSY represents a group having a chromophore group and consisting of a group of nonmetallic atoms necessary for cyclizing W and Z. ) General formula [■] Ar -N2 Formula [■], [rX], [X]
Includes compounds represented by

General formula [■] General formula [IX] General formula [X] Xa (wherein, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, B is a hydrogen atom or a methyl group, and A is a substituted or unsubstituted aryl group or represents a heterocyclic group, and n is 011 or 2.) Specific exemplary compounds of the general formula [■] include oxadiazole compounds having a benzofuran ring, such as those described in JP-A-54-74728. 2-trichloromethyl-5-(p-methoxystyryl)
-1,3,4-oxadiazole compounds and the like.

Further, as examples of compounds of the general formulas [rX] and [X], 4-(2
, 4-dimethoxy-4-styryl)-6-drichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-p-methoxystyryl-S-triazine compound, 2,4-bis- (trichloromethyl)-6-1
)-dimethylaminostyryl-S-triazine compounds and the like.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and a counter ion of an inorganic compound is recommended as the counter ion part. Specific examples include aromatic diazonium salts in which the 7-ion moiety of the diazonium salt is at least one of a fluoride ion, an arsenic fluoride ion, an antimony fluoride ion, an antimony chloride ion, a tin chloride ion, a bismuth chloride ion, and a zinc chloride ion. and preferably paradiazophenylamine salt.

The amount of the exposure visible image imparting agent contained in the total photosensitive layer composition is 0.01 to 20% by weight, preferably 0.1 to 20% by weight, and more preferably 0.2 to 10% by weight.

When these compounds having a trihaloalkyl group are added to the photosensitive layer, the change in erasability due to the change in the molecular weight of the polyhydroxy resin becomes more remarkable than when the compound is not added, which is interesting. However, the causal relationship is not clear.

' On the other hand, as the dye, any compound that forms a salt with a generally known acid can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like.

Specifically, Victoria Pure Blue BOH, Ethyl Violet, Crystal Violet, Brilliant Green, Pesic Tsukushin, Eosin, Phenolphthalein, Xylenol Blue, Congo Red, Malachite Green, Oil Blue #603, Oil Pink #
312, cresol red, auramine, 4-p-diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal violet, and the like. The amount of this dye added is approximately 0 in the total composition of the photosensitive layer.
．． 01 to 101i amount% is preferable, more preferably 0.01 to 101i amount%.
05~8! The amount is %.

Various other additives may be added to the photosensitive composition of the positive-working photosensitive lithographic printing plate of the present invention depending on various purposes. For example, to improve coating properties, surfactants such as cellulose alkyl ethers, fluorine surfactants, and silicone compounds are used, and phosphate esters, phthalate esters, polyvinyl butyl ether, etc. are used as physical property improvers of the coating film. In addition, various additives having hydrophobic groups such as p-octylphenol formalin novolac resin, p-t-butylphenol formalin novolak resin, p-t- Modified novolak resins such as butylphenol benzaldehyde resins and rosin-modified novolak resins are used, and O-naphthoquinonediazide sulfonic acid esters of these modified novolac resins (esterification rate of OH groups 20 to 70 mol%) are added. be able to.

The content of these additives varies depending on their type and purpose, but in general, the amount added is 0 to the total composition of the photosensitive layer.
．． 01-20% by weight, preferably 0.05-10% by weight
is appropriate. The photosensitive layer of the photosensitive lithographic printing plate of the present invention generally has a solid content of 0.5 to 3
．． 0 (1/f is appropriate.

The above-mentioned photosensitive composition is a coating material dissolved in various solvents, such as cellosolve agents such as methyl (ethyl) cellosolve and methyl (ethyl) cellosolve acetate, coating solvents such as dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, and trichloroethylene. It is formed by coating and drying on a grained and anodized aluminum plate support as described below.

When using the positive-working photosensitive lithographic printing plate thus obtained, a known method is applied, in which a positive-working film is brought into close contact with the plate, exposed to light using an ultra-high-pressure mercury lamp, a metal halide lamp, etc.
It is developed in an alkaline aqueous solution such as sodium metasilicate, potassium metasilicate, sodium phosphate, or caustic soda, and then supplied as a printing plate.

Burning treatment is also applied if necessary. The lithographic printing plates produced in this manner are used in sheet-fed and off-wheel printing presses.

The support provided with the photosensitive layer using the photosensitive composition of the present invention is an aluminum plate. When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing.

The various methods described above can be used alone or in combination depending on the composition of the aluminum material. Preferred is electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The formed anodic oxide film l is 1 to 50111 g/df
is appropriate, preferably 10 to 4011 g/df. For example, anodized oxide film Ill is produced by immersing an aluminum plate in a phosphoric acid chromic acid solution (85% phosphoric acid solution: 351J2, prepared by dissolving chromium oxide (■) = 20a in 12 parts of water) to form an oxide film. It is determined by measuring the weight change before and after the film on the plate melts.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 [Synthesis of photoreceptor] 400 g of p-hydroxyaniline, 411 hydroquinone monomethyl ether, 41 acetone, and 360 g of pyridine were mixed and cooled from the outside using a cryogen. When the internal temperature fell to -10°C, methacrylate was added. acid chloride 4
20 g was added dropwise while stirring. The dropping rate was adjusted so that the reaction temperature was 0°C or lower, and after the dropwise addition was completed, the mixture was stirred at 0 to 3°C for about 2 hours.

Next, after stirring at 25°C for 2 hours, the reaction solution was concentrated to 1/3, poured into 1 liter of diluted hydrochloric acid (1)H, and the resulting precipitate was suction-filtered. A white solid was obtained. This white solid was dissolved in warm methanol 21,
Furthermore, add 2r of 5% sodium carbonate aqueous solution and raise the temperature to 40°C.
The mixture was stirred for 30 minutes.

This dark red solution was then poured into 5% aqueous hydrochloric acid solution 82 to form a large amount of precipitate, which was filtered with suction and dried to give a pale pink solid. This was recrystallized from a mixed solvent of ethanol and water, and N-(4
-Hydroxyphenyl)acrylamide colorless needles 4
Obtained 50g.

21.1 g of the obtained N-(4-hydroxyphenyl)acrylamide was dissolved in 450 t12 of acetone, and 32 (l) of naphthoquinone-(1,,2)-diazide-(2>-5-sulfonic acid chloride) was added and dissolved. After that, 9.9g of potassium carbonate aqueous solution dissolved in 63ml of water was added dropwise.
The condensation reaction was carried out at 40-50°C for 40 minutes. After the reaction,
The reaction solution was diluted with hydrochloric acid (700tj2 of water, 3.5-d of concentrated hydrochloric acid)
The precipitated resin was collected by filtration and dried.

In this way, 0-naphthoquinonediazide sulfonic acid ester of N-(4-hydroxyphenyl)acrylamide (exemplified NO, (1)) 47 (l) was obtained.

Hereinafter, the obtained ester compound will be referred to as a "photoreceptor".

[Synthesis of binder] The above N-(4-hydroxyphenyl)acrylamide 1
06.4, acrylonitrile 32g, ethyl acrylate 7.2g, methyl methacrylate 73.2g
, and α,α′-azobisisobutyronitrile 6,56
(] to acetone/methanol (1:1) mixed solvent 300
After dissolving the mixture in a nitrogen solution and purging it with nitrogen gas, it was heated at 80° C. for 4 hours to obtain a polymer solution. Add this polymer solution to 5% of 32
Pour into HC1 aqueous solution, filter the resulting white precipitate,
Dry to form a white polymer (Example No. (1)) 195
I got atr. When the min molecule m was measured by GPC,
It was MW -3.5X 10 Gin.

Hereinafter, the obtained polymer will be referred to as "binder resin".

An aluminum plate with a thickness of 0.2411 was heated in a 5% sodium hydroxide aqueous solution at a temperature of 25°C and a current density of 60 A/df.
An electrolytic etching process was performed for a processing time of 3 seconds. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. The amount of anodic oxide film was 2011Mdf. Next, it was immersed in a hot aqueous solution at 90°C to seal the holes.

Subsequently, a photosensitive coating solution having the composition shown below was coated on the aluminum support using a spin coater and dried at 100° C. for 4 minutes to obtain a photosensitive lithographic printing plate (A).

(Photosensitive coating liquid composition) ・The above-mentioned photoreceptor [I] 1.8a・
The above-mentioned binder resin [116,6 g・p-tert
- Ester compound of novolak resin synthesized from octylphenol and formaldehyde and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride (condensation rate 50 mol%, weight average molecular weight 11 Mw -1
800) 0.084 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical ■) 0.084 g
- Ethyl cellosolve 671 g - Methyl cellosolve 33 coats The coating weight after drying was approximately 24 mg/df.

A step tablet for sensitivity measurement (N manufactured by Eastman Kodak Company) was placed on the thus obtained photosensitive lithographic printing plate <A).
8.0 using a 2KW metal halide lamp (Idolfin 2000 manufactured by Iwasaki Electric) as a light source.
Exposure was performed for 70 seconds at mW/cf.

When this sample was developed with a 4% potassium metasilicate aqueous solution at 25° C. for 45 seconds, the non-image area was completely removed and a lithographic printing plate was obtained. When the sensitivity was measured using the gray scale of the step tablet, it was found that the fourth stage was completely developed and became clear.

Next, in order to examine development tolerance (development latitude), we prepared a developer solution with a diluted alkali concentration and a developer solution with a higher alkali concentration than the standard 4% potassium metasilicate aqueous solution. Using the sample exposed for 70 seconds, the developability with a developer with reduced developing ability (under-developability) and the developability with a developer with excessive developability (over-developability) were examined. In examining the under-developability, the film was developed with 2.1% and 1.9% potassium metasilicate aqueous solutions at 25° C. for 45 seconds, and the solubility of the non-image area was determined. The more diluted the developer dissolves the photosensitive layer in the non-image area, the better the under-developability will be. In addition, in the study of over-developability, 6.0% potassium metasilicate aqueous solution was used at 25°C for 60 seconds and
% potassium metasilicate aqueous solution for 90 seconds at 25°C, and the number of solid steps (the lowest number of steps at which the photosensitive layer completely remains in the gray scale of the step tablet) was measured. The difference from the number of solid plates after standard development (4% aqueous potassium metasilicate solution, 25° C., 45 seconds) was determined. The smaller the difference in the number of solid steps is and the closer it is to standard development, the less erosion of unexposed areas and the better the over-development performance. Good development tolerance means that both under-development property and over-development property are good.

Furthermore, in order to examine resistance to processing chemicals, durability against plate cleaner and cleaning oil, which are used as a cleaning liquid to remove background stains that occur in non-image areas during printing, was investigated. The printing plate with the image with density difference on the gray scale steps mentioned above is removed using an FD plate cleaner (Toyo Ink Co., Ltd. a) or a UV plate cleaner (Moroboshi Ink Co., Ltd.).
12 hours in the stock solution of UV plate cleaning solution Best Cure (manufactured by Toka Shiki Kagaku ■) and Uv plate cleaning solution Trufit (manufactured by Clarei Soprene Chemical Co., Ltd.) for 10 minutes, and then washed with water. The degree of erosion of the image area to the treatment chemicals was measured by comparing it with the image area of .

The results of sensitivity, development latitude, and processing chemical resistance are shown in Table 1.

Comparative Example 1 The above-mentioned photoreceptor [I] was removed from the photosensitive coating liquid of Example 1, and instead, the 0-naphthoquinonediazide compound (photoreceptor [I]) described in Synthesis Example 1 of Japanese Patent Publication No. 50-24641 was used.
(2)) was coated on the same support as in Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (B).

The coated weight after drying was approximately 24+9/df.

Using this photosensitive lithographic printing plate (B), sensitivity, development latitude, and processing chemical resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The photosensitive coating liquid of Example 1 was prepared by removing the photoreceptor [I] described above and containing the following photoreceptor [III] manufactured by the same company instead, on the same support as in Example 1. A photosensitive planographic printing plate (C) was obtained by coating and drying in the same manner.

・Photoreceptor [I[[] Ester compound of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol acetone resin (weight average molecular fiMw -1000, condensation rate 30 mol%) The coated weight after drying was approximately 241 a/dv.

Using this photosensitive lithographic printing plate (C), sensitivity, development latitude, and processing chemical resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 From the photosensitive coating liquid of Example 1, the above-mentioned binder resin [
I], and instead use the same amount of the following binder resin [
A material containing I[] was coated on the same support as in Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (D).

・Binder resin [nl phenol, ■-cresol, p- copolycondensate novolak resin of cresol and formaldehyde (phenol: 1-cresol: p-cresol-20: 30: 50, weight average molecular weight MW-
7800) The coating weight after drying was approximately 241 Ω/dr.

Using this photosensitive lithographic printing plate (D), sensitivity, development latitude, and processing chemical resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 2 [Synthesis of photoreceptor] 104 g of hydroxyaniline, 0.5 g of hydroquinone monomethyl ether (1, 17 g of methacrylic anhydride)
After mixing 01J and 20G of water and reacting at 70°C for 2 hours, the mixture was cooled, and 5% hydrochloric acid 5oo112 was added thereto, and the resulting precipitate was filtered by absorption to obtain a white solid. After heating and dissolving this white solid in 5001 g of methanol, 5%
After adding 500 tQ of soda carbonate and stirring at 40°C for 30 minutes, the mixture was poured into 2 fl of 5% hydrochloric acid, a large amount of precipitate formed was filtered with suction, and then reconsolidated with ethanol to give a melting point of 171-17.
White crystals of l-hydroxymethacryanilide at 3°C 130! I got II.

The obtained hydroxymethacrylanilide zi,i
g was dissolved in 450 d of acetone, and naphthoquinone-(1,
2)-Diazido-(2)-5-sulfonic acid chloride 3
After dissolving 2 g, a potassium carbonate aqueous solution containing 9.9 g dissolved in water 63-112 was added dropwise, and a condensation reaction was carried out at 40 to 50° C. for 40 minutes. After the reaction, the reaction solution was poured into dilute hydrochloric acid (700 g of water, 3. hN of concentrated hydrochloric acid), and the precipitated resin was collected by filtration and dried.

In this way, 48 g of 0-naphthoquinonediazide sulfonic acid ester of N-(5-hydroxyphenyl)acrylamide [Exemplary Compound No. (2)] was obtained.

Hereinafter, the obtained ester compound will be referred to as "photoreceptor [■]".

[Synthesis of binder] The above N-(4-hydroxyphenyl)acrylamide (
HVI)MA) 53.2g, acrylonitrile (AN
) t5.9a, methyl methacrylate (MMA)4
0.09 and α,α'-azobisisobutyronitrile 0
．． 820 was dissolved in 190 mj2 of a mixed solvent of acetone:ethanol (1:2), and after purging with nitrogen gas, the mixture was heated to 65°C.
A polymer solution was obtained. This polymer solution was poured into an aqueous solution of 32 in 5% HC, and the resulting white precipitate was filtered and dried to obtain a white polymer 70Q. When the molecular weight was measured by GPC, it was Mn -3,2x103, My
-2.2x10+.

Hereinafter, the obtained polymer will be referred to as "binder resin [■]".

Example 1 The following photosensitive coating solution was applied to the same support as in Example 1.
The coating was applied and dried in the same manner as above to obtain a photosensitive planographic printing plate (E).

(Photosensitive coating liquid composition) - The aforementioned photoreceptor [IV] 1.8 (
+・The above-mentioned binder resin [III] 6
．． Ester compound of novolak resin synthesized from 60.p-tert-octylphenol and formaldehyde and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride (condensation rate 50 mol%, 1 m average molecular weight Mw -1,800) 0.08
4g Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.] 0.0841
;Tomethyl cellosolve 1001β
The coating weight after drying was approximately 241 g/df.

Using the photosensitive lithographic printing plate (E) thus obtained, sensitivity, development latitude, and durable processing chemical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Table 1 summarizes the results of sensitivity, development latitude, and processing chemical resistance for Example 1.2 and Comparative Examples 1 to 3.

In Table 1, Mark A indicates slight erosion in the image area.

Mark B indicates erosion as above, and the grains of the support under the photosensitive layer are slightly exposed.

Mark C shows significant erosion as above, and the grains of the support below the photosensitive layer are completely exposed.

It means that.

In addition, in terms of under-developability, ○ indicates that the photosensitive layer in the non-image area has been completely dissolved and removed.

Part of the Δ mark remains as above.

The X mark indicates that the same as above is hardly dissolved.

It means that.

Regarding over-developability, the numerical value means the difference in the number of solid stages from standard development, and the - mark means that the erosion of the image area is so severe that the over-developability is so bad that the number of solid stages can hardly be determined.

From the results of the above Examples and Comparative Examples, the following is clear. That is, from the comparison between Examples and Comparative Examples, when the photoreceptor [I] and photoreceptor [IV] of the present invention are used,
Compared to the conventional photoreceptors [I] and [I[], the binder resin [I] of the present invention has excellent over-developability and under-developability, and has a wide range of development latitude.
and [I[I] shows excellent processing chemical resistance.

(Effects of the Invention) As explained above, the photosensitive lithographic printing plate using the photosensitive composition of the present invention has excellent resistance to processing chemicals, especially resistance to plate cleaners and cleaning solutions used in UV ink printing. and has a wide range of development latitude.
It has excellent over-development and under-development properties.

Claims (1)

[Claims] (A) A compound having a structure represented by the following general formula [I] and the general formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 are each a hydrogen atom , represents a halogen atom, an alkyl group, an aryl group, a carboxyl group or a salt thereof, R_3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, R_1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, Y represents a divalent aromatic group that may have a substituent, X represents a divalent organic group, and n represents an integer of 0 to 5.) (B) Contains a phenolic OH group A photosensitive composition comprising a polymer having the unit in its molecular structure.