JPH07219214A - Photosensitive composition and photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To improve the sensitivity, plate wear resistance and adaptability to ball point pens by incorporating a reaction product of a specific compd. and an alkaline soluble resin into the compsn. CONSTITUTION:This photosensitive compsn. contains the reaction product of the compd. expressed by the formula and the alkaline soluble resin. In the formula, X1, X2 denote hydrogen atoms SO3Cl, 1 to 4c alkyl groups (may be straight chains or branched) or 6 to 18C aryl groups; X1, X2 may be the same or different but there is no case both are hydrogen atoms. The amt. of the reaction product to be added is preferably 5 to 60wt.%, more preferably 10 to 50wt.%. The alkaline soluble resin is exemplified by a novolak resin, vinyl polymer having a phenolic hydroxyl group, condensed resin of a polyvalent phenol and aldehyde or Ketone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate, and more particularly to a photosensitive composition having a reduced exposure time and a positive photosensitive lithographic printing plate. .

[0002]

BACKGROUND OF THE INVENTION Conventionally, positive-working photosensitive compositions used in the production of photosensitive lithographic printing plates and semiconductor integrated circuit devices include phenol-formaldehyde resin (usually referred to as novolac resin) and a photosensitive component. It consists of As the photosensitive component, an alkali-soluble resin such as pyrogallolacetone resin, or a compound obtained by esterifying 2,3,4-trihydroxybenzophenone and naphthoquinonediazide-5-sulfonyl chloride at the 5-position is usually used.

Further, this photosensitive composition is required to shorten the exposure time by increasing the sensitivity in working, and as a technique for solving this problem, naphthoquinonediazide-4 is used.
-There is a method of esterifying sulfonyl chloride. However, with this technology, naphthoquinone diazide-
4-Sulfonyl chloride has various drawbacks such as being less likely to be esterified than naphthoquinone-5-sulfonyl chloride, not being esterified to a high molecular weight alkali-soluble resin, and being likely to produce a reaction by-product.

Further, this technique has the drawback that the ballpoint pen is easily damaged and the printing durability is low.

[0005]

OBJECTS OF THE INVENTION Accordingly, the objects of the present invention are sensitivity, printing durability,
It is intended to provide a photosensitive composition and a photosensitive lithographic printing plate which are excellent in suitability for a ballpoint pen.

[0006]

The above objects of the present invention are: A photosensitive composition comprising a reaction product of a compound represented by the following general formula (1) and an alkali-soluble resin,

[0007]

[Chemical 3] [In the formula, X ₁ and X ₂ are hydrogen atoms, SO ₃ Cl, and carbon number 1
To 4 alkyl groups (which may be linear or branched) or aryl groups having 6 to 18 carbon atoms, and X ₁ and X ₂ may be the same or different, but both are hydrogen atoms. There is no. ]

2. A photosensitive lithographic printing plate having a photosensitive layer comprising a photosensitive composition containing a reaction product of a compound represented by the following general formula (1) and an alkali-soluble resin on a support;

[0009]

[Chemical 4] [In the formula, X ₁ and X ₂ are hydrogen atoms, SO ₃ Cl, and carbon number 1
To 4 alkyl groups (which may be linear or branched) or aryl groups having 6 to 18 carbon atoms, and X ₁ and X ₂ may be the same or different, but both are hydrogen atoms. There is no. ] Is achieved.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. The support used in the present invention is preferably one that withstands the flexibility and load that can be set in a normal lithographic printing plate, and a metal plate such as aluminum, magnesium, zinc, chromium, iron, copper or nickel, Examples thereof include alloy plates of these metals, and metal plates coated with chromium, zinc, copper, nickel, aluminum, iron or the like by plating or vapor deposition may be used. Of these, the preferred support is aluminum or its alloy.

The support used in the present invention is subjected to treatments such as degreasing treatment, graining treatment and anodizing treatment which are commonly used in this technical field. At least the graining treatment and the anodizing treatment are carried out. It is preferable to use a support prepared in this order.

Degreasing treatment for removing rolling oil on the aluminum surface includes solvent degreasing with trichlene and thinner, emulsion degreasing with kerosene and triethanol and the like. Further, in order to remove stains and natural oxide film which cannot be removed only by degreasing, an alkaline solution such as caustic soda having a concentration of 1 to 10% is added at 20 to 70 ° C. for 5 seconds to 10 seconds.
Examples include a method of dipping for a minute, then dipping in an acidic solution such as nitric acid or sulfuric acid having a concentration of 10 to 20% at 10 to 50 ° C. for 5 seconds to 5 minutes to perform neutralization and smut removal after alkali etching.

As a graining treatment method carried out for improving the adhesion to the photosensitive layer and improving the water retention,
There are a so-called mechanical surface-roughening method for mechanically roughening the surface and a so-called electrochemical surface-roughening method for electrochemically roughening the surface. Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, buff polishing and the like. The electrochemical surface-roughening method includes, for example, a method of electrolytically treating the support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. The support can be grained by using any one of these methods or a combination of two or more methods.

Since smut is formed on the surface of the support obtained by the graining treatment as described above, it is generally necessary to appropriately perform washing with water or alkali etching to remove the smut. preferable. Examples of such a treatment include the alkaline etching method described in Japanese Patent Publication No. 48-28123 and Japanese Patent Laid-Open No. 53-53.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in 12739.

The support used in the present invention has abrasion resistance,
An oxide film may be formed by anodic oxidation in order to improve chemical resistance and water retention. In this anodic oxidation, generally, an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% is used as an electrolytic solution and a current density is 1 to 10 A / d.
The method of electrolyzing with m ² is preferably used, but the method of electrolyzing with high current density in sulfuric acid described in US Pat. No. 1,412,768 and US Pat.
There is a method of electrolyzing using phosphoric acid described in Japanese Patent No. 1,661.

The support used in the present invention is preferably subjected to a surface treatment such as a pore-sealing treatment with hot water or the like or an immersion in an aqueous solution of potassium fluorozirconate after the anodizing treatment.

Then, a photosensitive layer containing the photosensitive composition of the present invention is applied onto the surface-treated support to obtain the photosensitive lithographic printing plate of the present invention. The photosensitive substances used in this photosensitive layer are described below.

The photosensitive composition of the present invention contains a reaction product of a compound represented by the following general formula (1) and an alkali-soluble resin, and also contains an alkali-soluble resin as a binder. The amount of the reaction product added is preferably 5 to 60% by weight, more preferably 10% by weight.
~ 50% by weight.

[0019]

[Chemical 5] [In the formula, X ₁ and X ₂ are hydrogen atoms, SO ₃ Cl, and carbon number 1
To 4 alkyl groups (which may be linear or branched) or aryl groups having 6 to 18 carbon atoms, and X ₁ and X ₂ may be the same or different, but both are hydrogen atoms. There is no. Examples of the alkali-soluble resin used in the present invention include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841, and the like. In addition to the above, those described later are also included.

Examples of the photosensitive composition of the present invention include:
Examples thereof include ester compounds of the compound represented by the general formula (1) and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and divalent catechol, resorcin, hydroquinone and the like. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred of these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin. To be

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the compound represented by the general formula (1) (reaction rate with respect to one OH group) is 1
5 to 80% is preferable, 20 to 45% is more preferable
Is.

The compound represented by the general formula (1) may be used alone or in combination with a conventional naphthoquinonediazide compound. As the o-quinonediazide compound preferably used in combination, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1,2-benzoquinone diazide sulfonic acid ester,
1,2-naphthoquinonediazide sulfonic acid ester,
1,2-benzoquinonediazide sulfonic acid amide, 1,
Known 1,2-quinonediazide compounds such as 2-naphthoquinonediazide sulfonic acid amides, more specifically by J. Kosar, "Light-Sensitive Systems" (Light-Sensitive).
Systems) pp. 339-352 (1965)
Year), John Willie & Sons (John
Willey & Sons (New York) and W S De Forest (WS De Fo)
rest) "Photoresist" (Photoresi)
st) Volume 50 (1975), McCraw Hill (Mc
1,2-Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, which is described in Graw Hill) (New York). 1,2-benzoquinonediazide-4- (N-ethyl-M-β-naphthyl) -sulfonamide, 1,2-
Naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-
Sulfonyl) -3,5-dimethylpyrazole, 1,2-
Naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-4'-azo-β-naphthol-ester, N, N-di- (1,2-naphthoquinonediazide-5
-Sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-
5-Sulfone-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonodiazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 , 4'-diaminobenzophenone 1 mol, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4,4'-dihydroxy-
Condensate with 1,1'-diphenylsulfone 1 mol, 1,
2-naphthoquinonediazide-5-sulfonic acid chloride 1
, 2-naphthoquinonediazide-5- (N-dihydroabietyl)-, a condensate of 1 mol of purpurogallin and 1 mol of purpurogallin
A 1,2-quinonediazide compound such as sulfonamide can be exemplified. In addition, Japanese Patent Publication No. 37-1953,
37-3627, 37-13109, 40-
No. 26126, No. 40-3801, No. 45-5604.
No. 45-27345, No. 51-13013, JP-A Nos. 48-96575, 48-63802 and 4
The 1,2-quinonediazide compounds described in JP-A No. 8-63803 can also be mentioned.

Of the above o-quinonediazide compounds, 1,
2-benzoquinone diazide sulfonyl chloride or 1,
An o-quinonediazide ester compound obtained by reacting 2-naphthoquinonediazidesulfonyl chloride with a pyrogallolacetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable. As the o-naphthoquinonediazide compound, the above compounds may be used alone or in combination of two or more kinds.

The novolac resin as the binder preferably used in the present invention is, for example, phenol.
Formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-57841, p- as described in JP-A-55-127553 Copolymer resins of substituted phenol and phenol or cresol and formaldehyde can be used.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and the weight average molecular weight Mw is 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0.
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more kinds.

The ratio of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight.

The vinyl copolymer having a phenolic hydroxyl group as a binder preferably used in the present invention is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and has the following general formula [I ] ~
Polymers containing at least one structural unit of [V] are preferred.

[0031]

[Chemical 6] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom.
R ₃ 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. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group 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 substituent. Represents a phenylene group or a naphthylene group which may have a substituent. ]

As the polymer, those having a copolymer type structure are preferable, and as the monomer unit which can be used in combination with the structural unit represented by each of the general formulas [I] to [V], For example, ethylene-based unsaturated offylenes such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and acrylics such as acrylic acid and methacrylic acid. Unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid, maleic anhydride, etc., such as methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, dodecyl acrylate, acrylic acid-
2-Chloroethyl, phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, and other α-methylene aliphatic monocarboxylic acid esters such as acrylonitrile and methacrylonitrile. Amides such as acrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m
-Anilides such as methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc., vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, chloride Vinyl, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1
Ethylene derivatives such as -methyl-1-nitroethylene,
For example, N-vinylpyrrole, N-vinylcarbazole,
There are N-vinyl type monomers such as N-vinyl indole, N-vinyl pyrrolidene and N-vinyl pyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Among the above monomers, aliphatic monocarboxylic acid esters and nitriles are preferable. These monomers may be bound to the polymer either in a block or random state.

The proportion of the vinyl polymer in the photosensitive composition is preferably 0.5 to 70% by weight.

As the vinyl-based polymer, the above polymers may be used alone or in combination of two or more kinds. or,
It can also be used in combination with other polymer compounds.

The photosensitive composition of the present invention is generally synthesized as follows.

Synthesis Example 1

[0038]

[Chemical 7]

Reaction; 1-hydroxynaphthalene-5-
100 g (0.41 mol) of sodium sulfonate and 67 g (0.49 mol) of zinc chloride are taken in 1 liter of methanol and refluxed for 3 hours. Remove the remaining zinc chloride by filtration,
After distilling off the solvent, 55.3 g of crude crystals are obtained. Yield 4
7.8%.

Reaction; thereafter, a conventional method for synthesizing naphthoquinonediazide, for example, a method described in the following references can be followed. a) W. Huber, Helv. Chem. Acta.
15, 1372 (1932) b) H.M. E. Fierz-David, L.S. Blan
gay ,: "Grundlegende Operat
ion der Farbenchemie ”, 7 u
changed edition, 173, Sp
Ringer Verlag, Wein (1947) c) H. Th. Bucherer, J .; parkt,
Chem. [2] 69, (1904) d) O.I. N. Witt, H .; Kaufmann, B
er. 24, 3157 (1891) e) J. Schmidt, W.A. Maier, ibi
d, 64, 767 (1931) f) M. P. Schmidt, US-Pat. Three
046, 118, Kale (1962)

Synthesis Example 2

[0042]

[Chemical 8]

Reaction; 1-hydroxynaphthalene-5-
100 g (0.41 mol) of sodium sulfonate and 67 g (0.49 mol) of zinc chloride are taken into 1 liter of n-propanol and refluxed for 3 hours. The residual zinc chloride was removed by filtration and the solvent was distilled off to obtain 5.78 g of crude crystals. Yield 46.2%.

Reaction; Thereafter, a conventional method for synthesizing naphthoquinonediazide, for example, the method described in the reference cited in Reaction 2 of Synthesis Example 1 above can be followed.

Synthesis Example 3

[0046]

[Chemical 9]

Reaction; 1-hydroxynaphthalene-5-
100 g (0.41 mol) of sodium sulfonate and 67 g (0.49 mol) of zinc chloride were added to iso-propanol 1
Reflux in liter for 3 hours. The remaining zinc chloride was removed by filtration and the solvent was distilled off to obtain 53.4 g of crude crystals. Yield 42.7%.

Reaction; Thereafter, a conventional method for synthesizing naphthoquinonediazide, for example, a method described in the reference cited in Reaction 2 of the above Synthesis Example 1 can be followed.

Synthesis Example 4

[0050]

[Chemical 10]

Reaction: 1-hydroxynaphthalene-5-
100 g (0.41 mol) of sodium sulfonate and 190 g (0.45 mol) of potassium iodide are dissolved with stirring in 1 liter of 40% ethylenediamine aqueous solution. 1. At room temperature
The reaction is complete after stirring for 5 hours. Dilute hydrochloric acid was added until the liquid became acidic and then extracted with methylene chloride to obtain 135 g of the desired compound. Yield 95.1%.

Reaction: 100 g (0.29) of sodium 1-hydroxy-4-iodonaphthalene-5-sulfonate
(Mol) in 750 ml of benzene while stirring under nitrogen for 30 minutes, irradiating with a xenon lamp, and further stirring for 24 hours.
After distilling off benzene, recrystallize with ethanol. 58 g of the expected compound are obtained. Yield 66.4%.

Reaction; Thereafter, a conventional method for synthesizing naphthoquinonediazide, for example, the method described in the reference cited in Reaction 2 of Synthesis Example 1 above can be followed.

The photosensitive composition of the present invention described above includes
It is possible to add a printout material that forms a visible image upon exposure. The printout material consists of an organic dye that changes its color tone by interacting with an acid or a compound that produces a free radical upon exposure to light.
Examples of the compound that generates an acid or a free radical upon exposure include o-type compounds described in JP-A-50-36209.
Naphthoquinonediazide-4-sulfonic acid halogenide, an ester compound of o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-53-36223 and a phenol having an electron-withdrawing substituent, or aniline acid. Or amide compounds, JP-A-55-7
Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A 7742, JP-A-57-148784 and the like.

As the above-mentioned organic dye, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), Oil Blue # 6
03 (manufactured by Orient Chemical Industry Co., Ltd.), Sudan Blue II
(Manufactured by BASF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green,
Examples thereof include Congo Red, Eosin, Rhodamine 66 and the like.

In addition to the above materials, the photosensitive composition also contains
If necessary, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added.

Further, in order to improve the oil sensitivity of the photosensitive composition, the photosensitive composition used in the present invention is, for example,
It is also possible to add a p-tert-butylphenol formaldehyde resin, a pn-octylphenol formaldehyde resin, or a resin in which these resins are partially esterified with an o-quinonediazide compound.

Each of these components was dissolved in the following solvent,
By coating and drying the support surface according to the present invention,
By providing a photosensitive layer, the photosensitive lithographic printing plate of the present invention can be manufactured.

Solvents that can be used when dissolving the photosensitive composition used in the present invention include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dicarboxylic acid methyl ether, dipropylene glycol methyl ethyl ether, Gi Ethyl, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, cyclohexanone , Methylcyclohexanone, diacetone alcohol, acetylacetone,
γ-butyrolactone and the like can be mentioned. These solvents are
They can be used alone or in combination of two or more.

As the coating method used for coating the surface of the support with the photosensitive composition, there are conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating. Coating or the like is used. At this time, the coating amount varies depending on the application, but for example, a coating amount of 0.05 to 5.0 g / m ² as a solid content is preferable. In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied, for example, a transparent original image having a line image, a halftone dot image, etc. is exposed in close contact with the photosensitive surface, Then, the relief image is obtained by removing the photosensitive layer in the non-image area with an appropriate developing solution. As a light source suitable for exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp or the like is used, and a developer used for the development is preferably an alkaline aqueous solution, for example, sodium silicate or potassium silicate. , Aqueous solutions of sodium hydroxide, potassium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and the like. The concentration of the alkaline aqueous solution at this time varies depending on the kind of the photosensitive composition and the alkali, but is generally in the range of 0.1 to 10% by weight, and the acid-alkaline aqueous solution may contain a surfactant or alcohol as necessary. It is also possible to add an organic solvent such as.

[0061]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was placed in a 5% by weight sodium hydroxide aqueous solution to form an aqueous solution.
After degreasing at 0 ° C. for 1 minute, the temperature was 25 ° C. and the current density was 60 A / d in 1 liter of 0.5 mol hydrochloric acid aqueous solution.
The electrolytic etching treatment was performed under the condition of m ² and the treatment time of 30 seconds. Then, after desmutting treatment in a 5 wt% sodium hydroxide aqueous solution at 60 ° C. for 10 seconds, in a 20 wt% sulfuric acid solution, the temperature is 20 ° C. and the current density is 3 A / d.
Anodizing treatment was performed under the conditions of m ² and treatment time of 1 minute.
Further, hot water sealing treatment was performed with hot water at 80 ° C. for 20 seconds to prepare an aluminum plate which was a support for a lithographic printing plate.

Photosensitive solution 1 having the following composition was applied to the support prepared as described above using a wire bar, and 8
It was dried at 0 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate sample 1 having a photosensitive layer. The thickness of the coating film after drying is 2.2 g / m.
It was ² .

[Photosensitive Solution 1] Novolac resin (phenol / m-cresol / p-cresol molar ratio of 10/54/36 and Mw of 4000) 6.7 g of Compound 1 (Synthesis Example 1) and pyrogallolacetone resin Condensate with (Mw3000) (esterification rate 35%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystil) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Methyl cellosolve 100 ml

Example 2 Compound 1 (Synthesis Example 1) of Photosensitive Solution 1 of Example 1 was replaced with Compound 2
Sample 2 was obtained in the same manner except that (Synthesis Example 2) was used instead.

Example 3 The compound 1 (Synthesis example 1) of the photosensitive solution 1 of Example 1 was replaced with the compound 3
Sample 3 was obtained in the same manner except that (Synthesis Example 3) was used instead.

Example 4 Compound 1 (Synthesis Example 1) of Photosensitive Solution 1 of Example 1 was replaced with Compound 4
Sample 4 was obtained in the same manner except that (Synthesis Example 4) was used.

Comparative Example 1 Compound 1 (Synthesis Example 1) of Photosensitive Solution 1 of Example 1 was mixed with 1,2-
Sample 5 was obtained in the same manner except that naphthoquinonediazide-5-sulfonyl chloride was used instead.

Comparative Example 2 An attempt was made to obtain a condensate of 1,2-naphthoquinonediazide-4-sulfonyl chloride and pyrogallolacetone resin by a conventional synthesis method, but none was obtained.

[Evaluation of Sensitivity] Examples 1 to 4 and Comparative Example 1
To the photosensitive lithographic printing plate samples 1 to 5 obtained in 1., a step tablet for sensitivity measurement (No. 2, Eastman Kodak Company, gray scale with a density difference of 0.15) was adhered, and a 2 kW metal halide lamp (Iwasaki Electric Co., Ltd.) Idol fin 2000) manufactured by the company was used as a light source, and exposure was performed for 40 seconds from a distance of 90 cm. Next, these samples 1 to 5 were developed with a 6-fold dilution of a developer (Konica's positive developer SDR-1) at 27 ° C. for 20 seconds, and the grayscale developed image obtained was completely processed. The number of clear stages being developed was calculated. The larger the number of clear steps, the higher the sensitivity. The results are shown in Table 1.

[Evaluation of Printing Durability] Each of Samples 1 to 5 obtained by the exposure and development described in the above-mentioned sensitivity evaluation was coated on a printing machine (Heidel GTO) with a coated paper printing ink (New Bright Red manufactured by Toyo Ink Mfg. Co., Ltd.). And fountain solution (Konica S
EU-3; 2.5%) is used for printing, and printing is continued until the solid part of the printed matter appears defective in ink or the non-image area is inked, and the number of printed sheets is counted. It was The results are shown in Table 1.

[Evaluation of suitability for ballpoint pen] Before development, a ballpoint pen for a register mark drawing machine (manufactured by Pilot) was used to draw on the unexposed area, and then the same development processing as in the above sensitivity evaluation was performed, and the drawn area was visually evaluated. (Erosion degree) was evaluated and determined as follows. The results are shown in Table 1. 6 points: Almost no erosion in the image area 4 points: Erosion in the image area 2 points: Significant erosion in the image area Note: The midpoint is an intermediate evaluation between the upper and lower parts.

[0072]

[Table 1]

[0073]

According to the present invention, it is possible to provide a photosensitive composition and a photosensitive lithographic printing plate which are capable of shortening the exposure time due to high sensitivity and which are excellent in ballpoint pen suitability and printing durability. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino City, Tokyo Konica Co., Ltd. (72) Inventor Fumiyuki Matsuo 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (2)

[Claims] 1. A photosensitive composition comprising a reaction product of a compound represented by the following general formula (1) and an alkali-soluble resin. [Chemical 1] [In the formula, X ₁ and X ₂ are hydrogen atoms, SO ₃ Cl, and carbon number 1
To 4 alkyl groups (which may be linear or branched) or aryl groups having 6 to 18 carbon atoms, and X ₁ and X ₂ may be the same or different, but both are hydrogen atoms. There is no. ] 2. A photosensitive lithographic plate comprising a support having thereon a photosensitive layer comprising a photosensitive composition containing a reaction product of a compound represented by the following general formula (1) and an alkali-soluble resin. Printed version. [Chemical 2] [In the formula, X ₁ and X ₂ are hydrogen atoms, SO ₃ Cl, and carbon number 1
To 4 alkyl groups (which may be linear or branched) or aryl groups having 6 to 18 carbon atoms, and X ₁ and X ₂ may be the same or different, but both are hydrogen atoms. There is no. ]