JPH04362644A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. for a photosensitive pianographic printing plate having excellent sensitivity. CONSTITUTION:In this photosensitive compsn. contg. a compd. capable of producing an acid under irradiation with active rays of light and a compd. having a bond which can be decomposed by the acid, the compd. capable of producing an acid under irradiation with active rays of light is a 2- halomethyl-1,3,4-oxadiazole compd. having at least an optionally substd. naphthofuryl group at the 5-position in a directly bonded state or through a vinyl group.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition for use in photosensitive lithographic printing, and more particularly to a photosensitive composition for photosensitive lithographic printing plates having excellent sensitivity.

0002

[Prior Art] In a photosensitive composition, exposed areas are solubilized in a developer through a first reaction in which an acid is generated by irradiation with actinic rays and a second reaction with the generated acid, that is, an acid decomposition reaction. Various methods are known that utilize this principle.

Various compounds and mixtures are known as acid-generating compounds involved in the first reaction. For example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF4-, PF6-, SbF6-, SiF6
--, ClO4-, etc., organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and organometallic/organohalogen compounds also have actinic radiation-sensitive components that form or separate acids upon irradiation with actinic radiation; All organic halogen compounds known as free-radical-forming photoinitiators are compounds that form hydrohalic acids.

Examples of compounds forming the above-mentioned hydrohalic acids are US Pat. No. 3,515,552 and US Pat.
, 536,489 and 3,779,778 and West German Patent Application No. 2,243,621; There is a compound that generates an acid by photolysis as described in No. 842.

[0005] Also, JP-A-54-74728, JP-A-55-24113, JP-A-55-77742, JP-A-60-3626, JP-A-60-13
2-halomethyl-1,3,4- described in Publication No. 8539
Specifically, oxadiazole compounds, etc., 2-trichloromethyl-5-[β(2-benzofuryl)vinyl]1
, 3,4-oxadiazole.

Furthermore, there is o-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-36209.

[0007]

However, the above-mentioned conventional photosensitive compositions have the disadvantage that the sensitivity is still insufficient.

That is, an object of the present invention is to provide a photosensitive composition for a photosensitive lithographic printing plate that has satisfactory and excellent sensitivity.

[0009]

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted extensive research and have developed a photosensitive composition comprising a compound that can generate an acid upon irradiation with actinic rays and a compound that has a bond that can be decomposed by an acid. In a product, a compound capable of generating an acid upon irradiation with actinic rays binds at least a substituted or unsubstituted naphthofuryl group directly or via a vinyl group.
It has been found that this can be achieved by using a 2-halomethyl-1,3,4-oxadiazole compound having a 2-halomethyl-1,3,4-oxadiazole compound.

More specifically, the 2-halomethyl-1,3,4-oxadiazole compound used in the present invention has a substituted or unsubstituted naphthofuryl group directly or via a vinyl group at the 5-position (hereinafter referred to as "the present invention"). Acid-generating compounds of the invention”
Preferably, those represented by the following general formula [I] can be mentioned.

[0011]

[Formula 1] In the formula, X represents a halogen atom, R1 represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, A represents a substituted or unsubstituted naphthofuryl group, and m represents 1
It is an integer of ~3, and n is 0 or 1.

In the above general formula [I], the halogen atom represented by X is preferably a chlorine atom or a bromine atom, and the alkyl group represented by R1 is a linear,
It may be branched or cyclic, and has 1 to 1 carbon atoms.
6 are preferred, and typical examples include:
Examples include methyl group, ethyl group, butyl group, and the like. Also R
A typical example of the aryl group represented by 1 is a phenyl group.

Examples of groups which may be substituted on the naphthofuryl group represented by A include hydroxyl group, alkyl group, alkoxy group, cyano group, nitro group, phenoxy group, phenyl group, halogen atom, amino group, and alkylamino group. etc. can be mentioned.

Specific examples of the acid-generating compound of the present invention are listed below, but the present invention is not limited thereto.

[0015]

[Case 2]

[0016]

[Chemical formula 3]

[0017]

[C4]

[0018]

[C5]

The acid generating compound of the present invention is preferably contained in the photosensitive composition in an amount of 0.01 to 20% by weight, more preferably 0.1 to 20% by weight.

In the present invention, other trihaloalkyl compounds or diazonium compounds may be used in combination with the acid-generating compound of the present invention to generate acids or free radicals upon irradiation with actinic rays, within a range that does not impair the effects of the present invention. Salt compounds can be used.

Next, a compound having at least one bond that can be decomposed by the acid generated by the acid generating compound of the present invention (
Hereinafter, the acid-decomposed compound of the present invention) will be explained.

The acid-decomposable compound of the present invention includes various known compounds and mixtures. For example, Japanese Patent Application Publication No. 48-
No. 89003, No. 51-120714, No. 53-13
No. 3429, No. 55-12995, No. 55-1262
Compounds having a C-O-C bond described in the specifications of No. 36 and No. 56-17345, JP-A-60-37
Compounds having Si-O-C bonds described in the specifications of No. 549 and No. 60-121446, JP-A-60
Other acid-decomposed compounds described in the specifications of No. 3625 and No. 60-10247. Yet another special request
Si-N described in the specification of No. 1-16687
Compounds having a bond, carbonic acid esters described in the specification of Japanese Patent Application No. 1983-94603, Japanese Patent Application No. 1982-58
Compounds having >C=N- bonds described in the specification of No. 149, ortho carbonic acid esters described in the specification of Japanese Patent Application No. 1983-251744, Japanese Patent Application No. 1987-1
Orthotitanate esters described in the specification of No. 25473, acetals and ketals described in the specification of Japanese Patent Application No. 155481/1983, Japanese Patent Application No. 1987-155481,
Compounds having a C--S bond described in the specification of No.-87769 can be mentioned.

Among these acid-decomposed compounds, in the present invention, the compounds disclosed in JP-A-53-133429 and JP-A-56-1734 are used.
No. 5, No. 60-37549, No. 60-121446, Japanese Patent Application No. 125473/1982 and Japanese Patent Application No. 15/1983
Those described in each specification of No. 5481 are preferred.

Further, specific examples of the acid-decomposable compound of the present invention and synthesis methods are described in each of the above-mentioned specifications.

The content of the acid-decomposed compound of the present invention is preferably 5 to 70% by weight, particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition of the present invention.

The acid-decomposed compounds of the present invention may be used alone or in combination of two or more.

Examples of synthesis of the acid-decomposed compound of the present invention are shown below.

<Synthesis Example 1> 1,1-dimethoxycyclohexane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 72.1 g (0.5 mol), triethylene glycol (manufactured by Kanto Kagaku Co., Ltd.) 7
5.1 g (0.5 mol) and p-toluenesulfonic acid 8
0 mg was reacted at 100°C for 1 hour with stirring, then the temperature was gradually raised to 150°C, and further reacted at 150°C for 4 hours.

Methanol produced by the reaction was distilled off during this period. After cooling, 500 ml of tetrahydrofuran and 2.5 g of anhydrous potassium carbonate were added, stirred, and filtered. The solvent was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off at 150° C. under high vacuum to obtain a viscous oily product D-1.

[0030]

[C6]

<Synthesis Example 2> 500ml of benzene containing 53.1g (0.5mol) of benzaldehyde (manufactured by Kanto Kagaku Co., Ltd.) and 75.1g (0.5mol) of triethylene glycol.
2.5 g of sulfuric acid was added to the solution, and the mixture was reacted under reflux for 20 hours. The reaction water produced by the reaction was separated as an azeotrope. After the reaction was completed, 25 g of anhydrous potassium carbonate was added, stirred at room temperature for 2 hours, and then filtered. Benzene was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off at about 150° C. under high vacuum to obtain a viscous oily product D-2.

[0032]

[C7]

<Synthesis Example 3> Methyl orthoformate 53.1g
and 55.8 g of 1,2,6-hexanetriol were reacted in the same manner as in Synthesis Example 1 to obtain polymer orthocarboxylic acid ester D-3 having the following structural unit.

[0034]

[Chemical formula 8]

<Synthesis Example 4> Thioglycerol 10.9g
(0.1 mol), 10.6 g (0.1 mol) of methyl orthoformate
mol) and p-toluenesulfonic acid as acid catalyst.
16 g (0.001 mol) was gradually heated while stirring for 5 hours, and the temperature was raised to 130° C. while distilling off methanol as a by-product. The amount of methanol distilled off was 8.6 g.

Thereafter, the reaction was stopped by cooling, 1.1 g of anhydrous potassium carbonate was added, and the mixture was filtered to obtain a colorless and transparent viscous liquid.

Next, this liquid is vacuumed (approximately 1 mmHg).
After drying at about 80° C. for 10 hours, about 16 g of orthothioformic acid ester D-4 having the following structural unit was obtained.

[0038]

[Chemical formula 9]

<Synthesis Example 5> p-xylylene glycol 3
A solution of 64.5 g of dichlorodimethylsilane in 150 ml of ethyl acetate was added dropwise to a mixture of 4.5 g of dichlorodimethylsilane, 48.6 g of tetraethylene glycol, 87 g of pyridine, and 600 ml of ethyl acetate at room temperature with stirring, and the mixture was stirred at 50° C. for 3 hours. continued. The generated pyridine hydrochloride was separated by filtration and 5% N
It was washed with aHCO3 aqueous solution and then with saturated brine. After drying the solution over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure.
A product, silyl ether polymer D-5, was obtained.

[0040]

[Chemical formula 10]

<Synthesis Example 6> 68.1 g of orthomethyl carbonate
, 89 g of 1,2,6-hexanetriol and 0.1 g of p-toluenesulfonic acid are gradually heated to 90° C. with stirring. After stirring at 90°C for 3 hours, the mixture is further gradually heated to 150°C over 3 hours. During this time, methanol produced by the reaction is distilled off. After cooling, 500 ml of tetrahydrofuran was added to the reaction product, followed by 3 g of anhydrous potassium carbonate, stirred, and then filtered. The solvent was distilled off from the filtrate under reduced pressure to obtain polymer orthocarbonate D-6 having the following structural unit.

[0042]

[Chemical formula 11]

In the present invention, in addition to the acid-generating compound of the present invention and the acid-decomposing compound of the present invention, it is necessary to use a novolac resin as a high molecular weight binder that is soluble in an alkaline aqueous solution.

Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin as described in JP-A-55-57841, and JP-A-55-57841. Examples include copolycondensate resins of p-substituted phenol and phenol or cresol and formaldehyde, as described in Japanese Patent No. 127553.

The molecular weight (polystyrene standard) of the novolak resin is preferably such that the number average molecular weight Mn is 3.00×
102 to 7.50×103, weight average molecular weight Mw is 1.
00×103 to 3.00×104, more preferably Mn
is 5.00×102 to 4.00×103, Mw is 3.0
It is 0x103 to 2.00x104.

Furthermore, a lipophilic resin may be added to the photosensitive composition of the present invention in order to improve the oil sensitivity of the photosensitive composition.

[0047] The lipophilic resin (hereinafter referred to as a liposensitizing agent) is, for example, a resin substituted with an alkyl group having 3 to 15 carbon atoms, as described in JP-A-50-125806. condensates of phenols and aldehydes,
Specifically, t-butylphenol formaldehyde resin or the like can be added. Further, a photosensitive resin obtained by condensing a lipophilic substituted phenol formaldehyde resin with a sulfonic acid chloride of o-quinonediazide can also be added. These oil sensitizing agents are preferably contained in an amount of 0.1 to 5% by weight of the photosensitive composition of the present invention.

In the photosensitive composition of the present invention, a photosensitive layer is provided by dissolving each of the above-mentioned components in the following solvents and coating and drying them on the surface of a suitable support. A photosensitive lithographic printing plate can be formed using the photosensitive composition of the invention.

Solvents that can be used to dissolve each component of the photosensitive composition of the present invention include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, 1,2-propanediol monomethyl Ether or its acetate, 1
, 2-propanediol monoethyl ether or its acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone and the like.

[0050] Alternatively, the method described in JP-A No. 60-208750, that is, the photosensitive composition is dissolved in an organic solvent,
A method of producing a photosensitive coating liquid by emulsifying and dispersing the organic solvent solution in water and then substantially removing the organic solvent can also be used.

[0051] As the coating method, a conventionally known method can be used.

The support on which the photosensitive layer is provided using the photosensitive composition of the present invention may be a metal plate made of aluminum, zinc, steel, copper, etc., or plated or plated with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include vapor-deposited metal plates, paper, plastic films, glass plates, paper coated with resin, paper covered with metal foil such as aluminum, and hydrophilic plastic films. Among these, preferred is an aluminum plate treated to make it hydrophilic. As a support for the photosensitive lithographic printing plate, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

In the present invention, the active light rays may be any light rays sufficient to cause the acid-generating compound of the photosensitive composition of the present invention to form an acid. As the means, a conventional exposure and printing apparatus can be used, for example, an apparatus for exposing with a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, or an apparatus for scanning exposure with a laser beam, etc. can be used as appropriate. It's okay to be rejected. The exposure amount can be appropriately selected within the range of 0.1 mJ to 2000 mJ.

The photosensitive lithographic printing plate is exposed and baked using the above-mentioned exposure and baking device, and then developed with a developer, leaving only the unexposed portions on the surface of the support to form a positive-positive type relief image.

[0055] Aqueous alkaline developers can be suitably used for developing the photosensitive lithographic printing plate, and examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, secondary Examples include aqueous solutions of alkali metal salts such as sodium phosphate and tribasic sodium phosphate.

[0056]

[Effects of the Invention] According to the present invention, a photosensitive composition for a photosensitive lithographic printing plate having excellent sensitivity could be obtained.

[0057]

[Examples] Specific examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of photosensitive lithographic printing plate sample] After degreasing a 0.24 mm thick aluminum plate (material 1050, tempering H16) in a 5% caustic soda aqueous solution at 60° C. for 1 minute. ,
In a 0.5 mol 1 liter aqueous hydrochloric acid solution, temperature: 25°C,
Electrolytic etching treatment was performed under the conditions of current density: 60 A/dm2 and treatment time: 30 seconds. Next, after desmutting in a 5% caustic soda aqueous solution at 60°C for 10 seconds, desmutting was performed in a 20% sulfuric acid solution at a temperature of 20°C and a current density of 3.
Anodic oxidation treatment was performed under the conditions of A/dm2 and treatment time: 1 minute. Furthermore, a hot water sealing treatment was performed with hot water at 30° C. for 20 seconds to produce an aluminum plate as a support for a lithographic printing plate material.

Next, a photosensitive composition coating solution having the following composition was applied to this aluminum plate using a rotary coater, and dried at 90°C for 4 minutes to form a positive photosensitive lithographic printing plate sample No. I got 1.

(Photosensitive composition coating liquid composition) - Acid decomposition compound *1

2.5 g・Novolac resin *2

5.8 g・Photoacid generator (compound of the present invention) *3
0.3 g Victoria Pure Blue BOH (
(manufactured by Hodogaya Chemical Co., Ltd.) 0.05g methyl cellosolve
100ml*
1 Compound (D-1) obtained in acid-decomposed compound synthesis example 1 *2 Copolymer resin of novolak resin m-cresol, p-cresol, and formaldehyde (mole ratio of m-cresol and p-cresol is 6:4) , Mw=7,200, Mw/Mn=5.
2) *3 Photoacid generator Acid generating compound of the present invention Exemplary compound No. (1)

0
Examples 2 to 4, Comparative Examples 1 and 2 Photosensitive compositions Photosensitive compositions were prepared in the same manner as in Example 1, except that the acid decomposition compound and photoacid generator in the coating solution were changed as shown in Table 1. Lithographic printing plate sample No. 2 to 6 were created.

The obtained photosensitive lithographic printing plate sample No.
A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., gray scale with 21 levels with a density difference of 0.15) was attached to each of Nos. 1 to 6, and a 4KW metal halide lamp (Idol manufactured by Iwasaki Electric Co., Ltd.) was attached. fin 2
000) was used as a light source and exposed from a distance of 80 cm. Next, this sample was developed at 25° C. for 30 seconds using a developer prepared by diluting SDR-1 (manufactured by Konica Corporation) 7 times with water.

Sensitivity was defined as the exposure time at which the 5.0 step of the step tablet was completely cleared.

Table 1 shows the results of sensitivity tests conducted on each sample.

As is clear from the results shown in Table 1, Examples 1 to 4 of the present invention have extremely superior sensitivity than Comparative Examples 1 and 2.

[0066]

[Table 1]

[0067]

[Chemical formula 12]

Claims (1)

[Claims] Claim 1: In a photosensitive composition comprising a compound capable of generating an acid upon irradiation with actinic rays and a compound having a bond decomposable by the acid, the compound capable of generating an acid upon irradiation with actinic rays is at least substituted with or a 2-halomethyl-1,3,4-oxadiazole compound having an unsubstituted naphthofuryl group directly or via a vinyl group at the 5-position.