JPH04122939A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the photosensitive compsn. having excellent processing chemical resistance and particularly an excellent UV ink characteristic and overdeveloping characteristic without degrading an inking property by incorporating a quinone diazide compd. and a vinyl resin and novolak resin having the glass transition temp. of the values within specific ranges. CONSTITUTION:This compsn. contains the quinone diazide compd., the vinyl resin having the glass transition temp. of the value within the 70 to 200 deg.C range and the novolak resin having the glass transition temp. of the value within the 30 to 100 deg.C range. The vinyl resin having the glass transition temp. of the value within the 70 to 200 deg.C range is exemplified by, for example, a vinyl resin having a carboxyl group. A novolak resin contg. 30 to 90mol% m-cresol is particularly preferable as the novolak resin having the glass transition temp. of the value within the 30 to 100 deg.C range.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive composition, and particularly to a photosensitive composition suitable for a photosensitive lithographic printing plate having excellent developability and processing chemical resistance.

[Prior Art and Problems to be Solved] 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 to form a final image, the non-image portion Ii1 is removed while leaving the image portion, so that an image is formed. In printing, the difference in properties of image areas being lipophilic and non-image areas being hydrophilic is utilized.

Positive-working photosensitive lithographic printing plates have low resistance to various processing chemicals used during printing, such as isopropyl alcohol contained in fountain solution, ink, surface preparation liquid, plate cleaner, etc. However, it has the disadvantage that printing durability is reduced.

In particular, the processing chemicals (especially washing oil, plate cleaners, etc.) used during printing using ultraviolet curable UV inks in recent years must be more powerful than the above processing chemicals, so they must be used as a binder. When ordinary novolac resins such as cresol novolac resins were used, the durability was insufficient.

Furthermore, Japanese Patent Publication No. 56-54621 discloses a photosensitive composition containing as a binder a resin obtained by copolycondensing phenol, p-mixed cresol, and aldehyde to improve processing chemical resistance. However, this resin also has extremely insufficient resistance to processing chemicals used in UV ink printing. Special Public Service 1977-
The photosensitive composition disclosed in Japanese Patent No. 28401 is described as containing a photoreceptor made of an 0-naphthoquinonediazide acid derivative and a binder made of a polymer compound containing p-hydroxymethacrylanilide or the like as a repeating structural unit. ing. Although the use of this binder improved the resistance to processing chemicals used in U-ink printing, it had the drawback of poor ink visibility.

On the other hand, the development of positive-working photosensitive lithographic printing plates as described above is usually carried out in a developer consisting of an alkaline aqueous solution, but the developing ability of the developer is subject to fluctuations under various conditions. Due to an excessive amount of replenishment or an increase in bath temperature due to a rise in temperature, the developing ability may exceed the specified value, and the image area of the printing plate may be eroded or the halftone dots may disappear.

For this reason, it is desirable that photosensitive lithographic printing plates have a wide range of development tolerance, showing the same developability as when processed with a standard developer, even with a developer whose processing capacity is enhanced compared to the standard developer. ing. (Hereinafter, the permissible range of increase in developing ability that provides appropriate development results will be referred to as "over-developability.") Therefore, the purpose of the present invention is to improve processing chemical resistance, especially for UV inks, without reducing ink visibility. The object of the present invention is to provide a photosensitive composition suitable for a photosensitive lithographic printing plate having excellent properties and excellent over-developability.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to provide a quinonediazide compound with a glass transition temperature (Tg) within the range of 70 to 200°C. It has been found that this can be achieved by providing a photosensitive composition containing a vinyl resin having a temperature of 30°C and a novolak resin having a glass transition temperature (Tg) of 30 to 100°C.

The present invention will be explained in more detail below.

The glass transition temperature (Tg) used in the present invention is 70~
Examples of the vinyl resin having a temperature within the range of 200° C. (hereinafter referred to as the vinyl resin of the present invention) include, for example, a vinyl resin having a carboxyl group, and the copolymer constituting the resin includes: For example, acrylic acids such as acrylic acid and methacrylic acid; vinyl copolymers synthesized with monomer components having carboxyl groups as essential components, such as unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride. One example is merging. In the copolymer, monomer components having a carboxyl group include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; examples include styrene, α-methylstyrene, p-methylstyrene, and p-methylstyrene; - Styrenes such as chlorostyrene: e.g. methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 12-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate , ethyl methacrylate, ethyl ethacrylate, and other α-methylene aliphatic monocarboxylic acid esters; for example, acrylonitrile, methacrylonitrile, and other nitriles; for example, acrylamide, N-(p-aminosulfonylphenyl)methacrylamide, N- Amides such as (p-methylaminosulfonylphenyl) methacrylamide; Imides such as N-phenylmaleimide; Anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide;
For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and β-chloroethyl vinyl ether; p-aminosulfonylphenyl methacrylate; vinyl chloride; Vinylidene chloride; vinylidene cyanide; for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1゜1-dimethoxycarbonylethylene,
Ethylene derivatives such as 1-methyl-1-ditroethylene; for example, N-vinylpyrrole, N-vinylrubazole, N-vinylindole, N-vinylvinylidene, N-
Preferred examples include vinyl monomers such as N-vinyl compounds such as vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

These monomers may be bound in the above-mentioned polymer compound in either a block or random manner.

The above polymers may be used alone or in combination of two or more. It can also be used in combination with other polymer compounds.

Furthermore, as the vinyl resin of the present invention, the following vinyl resins having phenolic hydroxyl groups can also be used. It is a combination and has the following formula [I] ~ [
A polymer containing at least one structural unit of VI] is preferably used.

-Formula [I] -+ CR1R2-CRs← 0-Co-B-OH General formula [I[] →CR1R2-CR3+ C0NR4→A+rB-OH General formula [1[[] %Formula% General formula [IV] +cR+ R2 -CRs+- -0H General formula [V] OH OH In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a carboxyl group, preferably a hydrogen atom. R3 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. R4 is a hydrogen atom, an alkyl group,
Represents an aryl group or an aralkyl group, preferably water
It is a g atom. A represents an alkylene group that may have a substituent that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, Kei represents an integer of O 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. In the present invention, among these, a copolymer containing at least one structural unit represented by formula [I] is preferred.

The vinyl resin preferably has a copolymer-type structure, and in such a copolymer, at least one structural unit represented by each of formulas [I] to [VI] and Single [1] that can be used in combination
Examples of the body unit include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene,
Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, acrylic ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 12-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide; , -anilides such as monomethoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, Ill vinyl, such as methyl vinyl ethyl, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether vinyl ethers such as vinyl chloride, nylidene chloride, and nylidene cyanide, such as 1-methyl-1-methoxyethylene,
Ethylene derivatives such as 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrol, N-vinylcarbazole, N-vinylindole, N There are vinyl monomers such as N-vinyl compounds such as -vinylvirolone and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds in m-structures in which unsaturated double bonds are cleaved.

Among the above monomers, (meth)acrylic acids, esters of aliphatic monocarboxylic acids, and nitriles are used in combination with at least one of the structural units represented by general formulas [I] to [VI]. shows excellent overall performance and is preferable. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like.

These monomers may be bonded to the vinyl resin in either a block or random manner.

General formulas [I] to [VI] in the vinyl resin
The content of the structural units represented by each of these is preferably 5 to 70 mol%, particularly preferably 10 to 40 mol%.

The above-mentioned polymers may be used alone or in combination of two or more thereof in the photosensitive composition.

Typical specific examples of vinyl resins used in the present invention are listed below. In the compounds exemplified below, MW is weight average molecular weight, Mn is number average molecular weight, s, f! ,
o, m and n each represent mol% of the structural unit.

Margin below Exemplary compound (b) CH.

CH.

CH.

('') CH.

The proportion of the vinyl resin in the photosensitive composition of the present invention is preferably 30 to 90% by weight, more preferably 40 to 85% by weight! 1%.

Furthermore, the photosensitive composition of the present invention has a glass transition temperature (Tg) of
is a value within the range of 30 to 100°C (
Hereinafter referred to as the novolak resin of the present invention),
In particular, fog-cresol of 30 to 9
Novolac resins containing 0 mol% are preferred. Such novolac resins are copolycondensates of phenols and active carbonyl compounds, and the phenols must contain 30 to 90 mol%, preferably 40 to 80 mol% of -cresol based on the novolak resin. be.

In addition, the phenols that are copolycondensation components with the above-mentioned -1-cresol include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specifically, for example, phenol , 0-cresol,
p-cresol, 3゜5-xylenol, 2.4-xylenol, 2゜5-xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, or alkyl group (1 to 8 carbon atoms) substituted Examples include phenol, preferably phenol, O-cresol, or p-cresol.

The active carbonyl compounds include, for example, aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Specific examples of the novolac resin of the present invention include phenol/enteric-cresol/formaldehyde copolycondensate resin, 0-cresol/--cresol/formaldehyde copolycondensate resin, -mono-cresol/p-cresol/formaldehyde copolycondensate resin, etc. Polycondensate resin, 0-cresol
Preferred examples include -cresol/p-cresol/formaldehyde copolycondensate resin and phenol/cresol/p-cresol/formaldehyde copolycondensate resin.

The most preferred novolac resin in the present invention is ■ -cresol/p-cresol/formaldehyde copolycondensate resin consisting of -cresol, p-cresol, and formaldehyde, or phenol/p-cresol/ρ
- A phenol/l-cresol/p-cresol/formaldehyde copolycondensation resin consisting of talesol and formaldehyde.

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

The molecule ff1 (polystyrene standard) of the novolak resin of the present invention preferably has a number average molecular weight (Mn) of 3.00.
X i Q2 ~ 7.50 X l Q3, weight average molecular weight (Mw) is 1.00 x 1 Q3 ~ 3.0O
XiO→More preferably Mn is 5.00×102~
4.00 x 103, MW is 300 x 103 ~ 2.00
It is a value within the range of X 10'.

The molecular weight of such novolac resins can be measured using GPC (
It is carried out by gel permeation chromatography method). The number average molecular weight fflMn and the weight average molecular weight MW are calculated by smoothing the peaks in the oligomer region by the method described in Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, "Journal of the Chemical Society of Japan," pages 800 to 805 (1972). This method shall be used to connect the center of the peak and the center of the valley.

In addition, in the novolac resin of the present invention, a method for confirming the quantitative ratio of phenols used in its synthesis is as follows:
Pyrolysis gas chromatography
-gaschromatography, PGC
) is used. Regarding pyrolysis gas chromatography, its principles, equipment, and experimental conditions can be found, for example, in the Journal of the Chemical Society of Japan, Tsuge Shin's New Experimental Chemistry Course, Vol. 19, Polymer Chemistry [I], pp. 474-485 (Maruzen 1978). The method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in Morio Tsuge, Takashi Tanaka, and Masayuki Tanaka, Analytical Chemistry, Vol. 18, pp. 47-52 (196
9).

Moreover, the content of the novolak resin of the present invention contained in the photosensitive composition is preferably 3 to 60% by weight, more preferably 5 to 50% by weight.

The quinonediazide compound in the present invention is preferably an O-naphthoquinonediazide compound, and as such, an ester compound of O-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones is preferably used.

Examples of the phenols include phenol, 0-
Cresol, bait-cresol, ρ-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Further, examples of the ketone include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, p-cresol/formaldehyde resin, ■-cresol/formaldehyde resin, -1, ρ-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/acetone. Examples include resin.

The condensation rate of O-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol in the O-naphthoquinonediazide compound (reaction rate with respect to 0 groups) is preferably 15 to 80%, more preferably 20 to 60%.

Further, as the quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, known 1,2-quinonediazide compounds such as 1.2-naphthoquinonediazide sulfonic acid ester and 1,2-naphthoquinonediazide sulfonic acid amide, and more specifically, known 1,2-quinonediazide compounds such as 1.・Sensitive
``Light-Sensit''
ive 3 ystevs” n #1 33
pp. 9-352 (1965), John Wiley & Sons
) New York) and W Varnish D-Ft.
Rest (W, S, [)e Forest) f,
Fyr Tresisto J (”Photoresi
50, (1975), McGraw-Hill Co., Ltd. (New ml-
1,2-naphthoquinonediazide described in
5-sulfonic acid cyclohexyl ester, 1-(1,2
-naphthoquinonediazide-5-sulfonyl)-3,5-
Dimethylpyrazole, 1,2-naphthoquinonediazide-
5-Sulfonic acid-4″-hydroxydiphenyl-4″-azo-β-naphthol ester, N,N-diku1,2-
naphthoquinonediazide-5-sulfonyl)-aniline,
2'-(1,2-naphthoquinonediazide-5-sulfonyloxy)-1-hydroxy-anthraquinone, 1,2
-Naphthoquinonediazide-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfone l! -2,3,4-trihydroxybenzophenone ester, 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'
- condensate of 1 mol of diaminobenzophenone, 2 mol of 1.2 naphthoquinonediazide-5-sulfonic acid chloride and 4
, 1 mole of 4'-dihydroxy-1,1'-diphenylsulfone condensate, 1,2-naphthoquinonediazide-5
- 1,2-1 such as a sulfonic acid chloride 1 mole and purbrogalin 1 mole, 1,2-natoquinone diazide-5-(N-dihydroabiethyl)-sulfonamide, etc.
Examples include nondiazide compounds. Also, Special Publication No. 37-1953, No. 37-3627, No. 37-1
No. 3109, No. 40-26126, No. 40-380
No. 1, No. 45-5604, No. 45-27345, No. 51-130134, JP-A No. 48-96575, No. 4
The 1°2-quinonediazide compounds described in No. B-63802 and No. 48-63803 can also be mentioned.

Furthermore, examples of the quinonediazide compounds used in the present invention include 1,2-naphthoquinonediazide-4-sulfonic acid cyclohexyl ester, 1(1,2-naphthoquinonediazide-4-sulfonyl)-3,5-dimethylpyrazole, and 1.2-naphthoquinonediazide-4-sulfonic acid cyclohexyl ester. -naphthoquinonediazide-4-sulfone I
I -4''-hydroxydiphenyl-4''-azo-β-
Naphthol ester, 2'-(1,2-naphthoquinonediazide-4-sulfonyloxy)-1-hydroxy-
Anthraquinone, 1,2-naphthoquinonediazide-4-
Sulfone 1ift-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-4-sulfonic acid-2,3,4-1-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-4-sulfone 1f-2,3 , 4'4'-tetrahydroxybenzophenone ester, 1,2-naphthoquinone diazide-4
- 2 moles of sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-1゜1'-diphenylsulfone, 1゜2-naphthoquinonediazide-4-sulfonic acid chloride 1
1,2-nanotoquinone-2-diazide-4- of a polyhydroxy compound such as a sulfate of 1 mole of purbrogalin and 1 mole of purbrogalin.
Examples include sulfonic acid ester compounds.

Furthermore, an O-naphthoquinone cyazide sulfonic acid ester compound of a polyurethane resin as shown in 2 below may also be used.

Margin below (however, n is 2~ An integer of 300 is a momme.

Further, in the present invention, an ester compound of a vinyl polymer having a phenolic hydroxyl group and 0-naphthoquinonediazide sulfonic acid can also be used. The vinyl polymer having a phenolic hydroxyl group that forms such an ester compound is a polymer having a unit having phenolic water MW in its molecular structure, and preferably the phenol used as the vinyl resin of the present invention. The same vinyl polymers as those having a hydroxyl group can be used.

As the quinonediazide compound used in the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination. The proportion of the quinonediazide compound used in the present invention in the photosensitive composition is 5 to 60% by weight.
is preferred, particularly preferably 10 to 50% by weight.

The photosensitive composition of the present invention may further contain an m-acid or an acid anhydride, if necessary.

As the organic acid that can be used in the present invention, various known organic acids can be used, including those with a pKa value of 2 or more.
is preferred, more preferably an organic acid having a pKaf of 30 to 90, particularly preferably 35 to 8.0. However, the pKa value used in the present invention is a value at 25°C.

Examples of such organic acids include Chemistry Handbook group a! Edit ■
(Maruzen #1966, pages 1054-1058), all compounds that can exhibit the pKafi of the present invention can be mentioned. Examples of such compounds include benzoic acid, adipic acid, azelaic acid, isophthalic acid, p-toluic acid, qt-ruic acid, β-ethylglutaric acid, I-oxybenzoic acid, p-oxybenzoic acid, 3,5-dimethylbenzoic acid, 3,4-dimethoxybenzoic acid, glyceric acid, glutaconic acid, glutaric acid, p-anisic acid, succinic acid, sebacic acid, β, β~
Diethylglutaric acid, 1.1-cyclobutanedicarboxylic acid, 1.3-cyclobutanedicarboxylic acid, 1゜1-cyclopentanedicarboxylic acid, 1.2-cyclopentanedicarboxylic acid, 1.3-cyclopentanedicarboxylic acid, β,
β-dimethylglutaric acid, dimethylmalonic acid, α-tartaric acid, speric acid, terephthalic acid, pimelic acid, phthalic acid, fumaric acid, β-propylglutaric acid, propylmalonic acid, mandelic acid, mesotartaric acid, β-methylglutaric acid.

β, β-methylpropylglutaric acid, methylmalonic acid,
Malic acid, 1.1-cyclohexanedicarboxylic acid, 1.
2-cyclohexanedicarboxylic acid, 1.3-cyclohexanedicarboxylic acid, 1.4cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid,
Examples include erucic acid, undecenoic acid, lauric acid, n-capric acid, pelargonic acid, and n-undecanoic acid. Other compounds having an enol structure such as Meldrum's acid and ascordonic acid can also be preferably used. The proportion of the organic acid in the photosensitive layer is 0.05 to 10
Weight % is suitable, preferably 0.1 to 5 weight %.

Further, as the acid anhydride that can be used in the present invention, all known various acid anhydrides can be used, but cyclic acid anhydrides are preferable, such as phthalic anhydride, tetrahydrophthalic anhydride, etc. , hexahydrophthalic anhydride, 3,6-nindooxy-△-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, glutaric anhydride, maleic anhydride, chloromaleic anhydride, α-
) Fomaleic anhydride, succinic anhydride, pyromellitic acid, etc. These acid anhydrides are present in the photosensitive layer.
It is preferably contained in an amount of 5 to 10% by weight, particularly 01 to 5% by weight.

The photosensitive composition of the present invention can preferably contain a compound that generates an acid or a free radical upon exposure to light, and examples of such compounds include the following formulas [■] and [■], respectively. The trihaloalkyl compounds or diazonium salt compounds shown are preferably used.

General formula [Vlco (wherein, Xa represents a trihaloalkyl group having 1 to 3 g of carbon atoms, W represents each atom of N, S, Se, , P, and C, and Z represents 0.N, S, Indicates each atom of Se and P.Y
has a chromophore group and represents a nonmetallic atomic group necessary for cyclizing W and 7. However, the ring formed by the nonmetallic atom group may have the above-mentioned Xa. ) General formula [■] Ar -N2 Below - Formula [■], [X] or [X
I].

- Formula [IX] General formula [X] General formula [1] (wherein, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, L is a hydrogen atom or a methyl group, and J is a fit-substituted or unsubstituted aryl group) or represents a Wt elementary ring group, and n is 0
．． 1 or 2. ) - Specifically, the compound represented by the formula [rX] includes an oxadiazole compound having a benzofuran ring such as
2-trichloromethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
3,4-oxadiazole compound or the following compound described in JP-A-60-241049: The following compound described in JP-A-54-74728: The following compound described in JP-A-55-77742: 1986
The following compound described in Publication No.-3626: JP-A-60-17
The following compound described in Publication No. 7340: JP-A-61-143
The following compound-2 described in No. 748 can be mentioned.

In the margins below, the compound represented by formula [X] or [XI] is specifically 4-(2,4-dimethoxy-4-styryl) described in JP-A-53-36223. -6-Dolichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-p-methoxystyryl- described in JP-A-48-36281
S-triazine compounds, 2<4>-bis-(trichloromethyl)-6-p-dimethylaminostyryl-8-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 of such compounds include aromatic compounds in which the anion moiety of the diazonium salt is at least one of the following: sulfur fluoride ion, arsenic fluoride ion, antimony fluoride ion, andymonium chloride ion, tin chloride ion, bismuth chloride ion, and zinc chloride ion. Examples include group diazonium salts, and preferably diazophenylamine salts.

The amount of the compound that produces acid or MlllM upon exposure in the total photosensitive layer composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 201% by weight, particularly preferably 02 to 10% by weight. %.

The photosensitive composition of the present invention preferably contains, together with the above-mentioned compound that generates an acid or a free radical upon exposure to light, a color change agent that changes the color tone by interacting with the photodecomposition product. There are two types of such color changing agents: those that develop color and those that fade or change color. As the color-changing agent that causes fading or discoloration, various dyes such as diphenylmethane, triphenylmethane-based thiazine, oxazine-based, xanthine-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes are effectively used.

Specific examples of these include the following: Brilliant Green, Eosin, Ethyl Violet, Erythrosin B1 Methyl Green, Crystal Violet, Pesic Tsuksin, Phenolphthalein, 1,3-Diphenyltriazine, Alizarin Red S1 Thymolphthalein, Methyl Violet 2B
, Quinaldine Red, Rose Bengal, Metanyl Yellow Thymol Sulfophthalein, Xylenol Blue Methyl Orange, Orange■, Diphenylthiocarbazone,
2,7-dichlorofluorescein, rose methyl red,
Congo red, benzobrulin 4B, α-naphthyl red, dill blue 281 Nile blue A, phenacetalin, methyl violet, malachite green, paratuxin, Victoria pure blue BOH (manufactured by Odugaya Kagaku n), oil blue #603 [Orient Chemical Industry Co., Ltd.] "Made by ■", Oil Pink #312 [Made by Orient Chemical Industry ■], Oil Red 5B [Made by Orient Chemical Industry ■]
, Oil Blue Let #308 [Orient Chemical Engineering 1a
[Made by Aji], Oil Red OG [Made by Orient Chemical Industry ■]
, Oil Red RR [Orient Chemical Industry] 1, Oil Blue #5o2 [manufactured by Orient Chemical Industry ■, Subiron Red BEH Special [manufactured by Hodogaya Chemical Industry ■],
-Cresol Purple, Cresol Red, Rhodamine 810-Damine 6G1 Fast Acid Violet R1 Sulforhodamine B1 Auramine, 4-1-Diethylaminophenylimino Naphthoquinone, 2-Carboxyanilino-4-1-Diethylaminophenylimino Naphthoquinone, 2- Carbostearylamino-4-p-dihydroxyethylamine-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamine-
〇′-Methylphenyliminoacetanilide, cyano-
p-diethylaminophenyliminoacetanilide, 1
-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-
1) -Diethylaminophenylimino-5-pyrazolone.

Moreover, arylamines can be mentioned as color-changing agents that develop color. Arylamines suitable for this purpose include not only simple arylamines such as primary and secondary aromatic aminos but also so-called leuco dyes, examples of which include the following.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl p-phenylenediamine, p-toluidine, 44'-biphenyldiamine, 0-chloroaniline, 0-bromoaniline, 4-chloro-〇-phenylenediamine, 0- Bromo-N, N-
Dimethylaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N-methyldiphenylamine, 0-toluidine, p,p'-tetramethyldiaminodiphenylmethane, N,N dimethyl -p-phenylenediamine, 1,2-dianilinoethylene, p, p
',p''-hexamethyltriaminotriphenylmethane, p,p'-tetramethyldiaminotriphenylmethane, p.

p″-tetramethyldiaminodiphenylmethylimine,
p, p', p''-triamino-0-methyltriphenylmethane, p, p', pN-driaminotriphenylcarbinol, p, p' -tetramethylaminodiphenyl-4-anilinonaphthylmethane, p, p', p''-triaminotriphenylmethane, p, p', p
″-hexapropyltriaminotriphenylmethane.

In the present invention, among the above-mentioned color change agents, dyes that can change color in DH regions 1 to 5 are preferred.

The proportion of the above color change agent in the photosensitive composition is 0.0
It is preferably used in an amount of 1 to 10% by weight, more preferably 0.02 to 5% by weight.

The photosensitive composition of the present invention preferably contains a condensation resin of a substituted phenol and an aldehyde represented by the following formula [■] and/or an 0-naphthoquinonediazide sulfonic acid ester compound of the resin.

- Formula [■] (In the formula, R5 and R6 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R7 represents an alkyl group or cycloalkyl group having 2 or more carbon atoms.) In the above general formula [■] In the substituted phenols represented, R5 and R6 are each a hydrogen atom, an alkyl group (including those containing 1 to 3 carbon atoms; alkyl groups having 1 to 2 carbon atoms are particularly useful), or halogen. represents an atom (among fluorine, chlorine, bromine and iodine atoms, chlorine and bromine atoms are particularly preferred), and R7 represents an alkyl group having 2 or more carbon atoms (preferably having 15 or less carbon atoms; Particularly useful are alkyl groups of numbers 3 to 8) or cycloalkyl groups (
Includes those containing 3 to 15 carbon atoms. C3 -C8 cycloalkyl radicals are particularly useful. ) represents.

Examples of the substituted phenols include isopropylphenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert=octylphenol, cyclohexylphenol, 3-methyl-4
-Chloro-5-tert-butylphenol, isopropylcresol, tert-butylcresol, tert
t-amyl cresol, hexyl cresol, tert
-octyl cresol, cyclohexyl cresol and the like, among which particularly preferred are tert-octylphenol and tert-butylphenol.

Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde, and furfural, including those having 1 to 6 carbon atoms. Among them, formaldehyde and benzaldehyde are preferred.

The resin obtained by condensing the substituted phenol and aldehyde in the present invention is synthesized by polycondensing the substituted phenol represented by the formula [■] and the aldehyde in the presence of an acidic catalyst. Inorganic acids and organic acids such as hydrochloric acid, oxalic acid, sulfuric acid, and phosphoric acid are used as acidic catalysts, and the blending ratio of substituted phenols and aldehydes is 1 part by mole of substituted phenols. On the other hand, aldehydes are 07-1
．． 0 mole part is used. Alcohols, acetone, water, tetrahydrofuran, etc. are used as the reaction solvent.

Predetermined temperature (-5~120℃), predetermined time (3~48v#
After the reaction, the reaction product is obtained by heating under reduced pressure and washing with water to remove ascites, or by condensation with water.

The 0-naphthoquinonediazide sulfonic acid ester compound of the polymerized resin of substituted phenols and aldehydes of the present invention can be obtained by dissolving the condensed resin in a suitable solvent, such as dioxane, and adding 〇naphthoquinonediazide sulfonic acid chloride thereto. It is obtained by esterification by adding an alkali such as an alkali carbonate dropwise to the equivalence point while heating and stirring.

In the esterified product, the condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to the hydroxyl group of the phenol (reaction rate % with respect to one hydroxyl group) is 5 to 80%.
is preferable, more preferably 20 to 70%, still more preferably 30 to 60%. The condensation rate can be calculated by determining the content of sulfur atoms in the sulfonyl group by elemental analysis.

The amount of the resin obtained by condensing the substituted phenol and aldehyde represented by formula [■] and the 0-naphthoquinonediazide sulfonic acid ester compound of the resin in the photosensitive composition of the present invention is 0.05 ~15M''% is preferable, particularly preferably 1~10% by weight, and the weight average molecular weight IMw is preferably 5.0X1Q2~5.0X10
3, more preferably 7. Ox 1Q 2~
The range is 3.0×103. The number average molecule IMn is preferably in the range of 3.0X1Q2 to 2.5X1Q3, more preferably 4.0X1Q2 to 20X103
is within the range of

The above molecular groups are measured by GPC method.

Calculation of number average molecular IMn and weight average molecular group MW is described in Morio Tsuge, Ichiya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan” 80
According to the method described on pages 0 to 805 (1972), the peaks of the oligomer region are leveled (the centers of the peaks and valleys are connected).

The photosensitive composition of the present invention can also contain a compound having at least one of the following structural units [D] and [E] in its molecular structure.

Structural unit [D] +CH2CH2O bar structural unit [EcoC)-13 1+CH2CH-O+- (In the formula, n represents an integer from 2 to 5000 T,) The structural unit [D] used in the present invention and The compound having at least one kind of [E] may be any compound having 10,000 or both of the above structural units [D] and [E], but in particular, compounds having n in the range of 2 to 500o may be used. Preferably, the compound is an integer and has a boiling point of 240"C or higher, more preferably a compound where 0 is an integer in the range of 2 to 500, and the boiling point is 280"C or higher, and the most preferred is n is a compound within the range of 3 to 1oo.

Examples of such compounds include -ho! J Echiμ>ri')]-ru(HO-+CH,C
H,C)7rr) Polyoxyethylene alkyl ether (R○(CH,C)(20)nH) Polyoxyethylene alkylphenyl ether Polyoxyethylene polystyrylphenyl ether Polyoxyethylene-polyoxypropylene glycol (However, this includes block polymers and random polymers) ・Polyoxyethylene-polyoxypropylene alkyl ether (terminals form an alkyl ether) (However, includes random polymers) ・Ethylene oxide derivatives of alkylphenol formalin condensates・Polyoxyethylene polyhydric alcohol fat 117i1! Examples of partial esters include polyoxyethylene fatty acid ester (eg, RC○○(CH2CH20)nH), polyoxyethylene alkylamine, and the like.

Specifically, the following are preferable, for example.

Namely, polyoxyethylene lauryl ether, boxoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Sorbitan monolaure~1~, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, tetraoleic acid polyoxyethylene sorbitol,
Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxypropylene block copolymer, polyethylene glycol, tetraethylene glycol, etc. be.

The proportion of the compound having at least one of the above structural units [D] and [E] in the photosensitive composition is preferably 01 to 20ffl1%, more preferably 02 to 10% by weight based on the total composition. .

Further, the above compounds may be used alone or in combinations of 211 or more, as long as they are within the range of the above content i.

In addition to the above-mentioned materials, the photosensitive composition of the present invention may further contain pigments such as dyes and pigments, sensitizers, plasticizers, surfactants, etc., if necessary.

Furthermore, by dissolving each of these components in the following solvent and further applying and drying this on the surface of a suitable support,
A photosensitive layer can be provided to form a photosensitive lithographic printing plate.

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, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, Examples include cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more.

The coating method used for coating the surface of the support with the photosensitive composition of the present invention includes conventionally known methods, such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating. Coating etc. are possible. At this time, the coating t varies depending on the application, but for example, the solid content is 05 to 5. OQ/f is preferred.

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

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 and brushing. iIl polishing method, polishing method using liquid honing, buffing method! Laws etc. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

Preferred is a method using electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, tim acid, FA 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 amount of anodized skin i formed is 1 to 50 I+g, /
d, + is appropriate, preferably 10 to 40 mg/dr
It is. The amount of anodized film can be determined by, for example, dipping an aluminum plate in a phosphoric acid chromic acid solution (85% phosphoric acid solution: 351 g, 1 chromium oxide (■): 20 o dissolved in 11 parts water) to dissolve the oxide film. , which can be determined by measuring changes in weight before and after dissolving the film on the plate.

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 with a water-soluble polymer compound or an aqueous solution of a gold B salt such as fluorinated zirconate.

The photosensitive lithographic printing plate to which the photosensitive composition of the present invention is applied is:
It can be developed using a conventional method.

For example, the transparent positive film is exposed to light from a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, and then developed with various alkaline developers. As a result, only the unexposed portion remains on the surface of the support, forming a positive-positive relief image.

Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, mM sodium, potassium carbonate,
Examples include aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate. The concentration of alkali metal salt is 0.
1 to 10% by weight is preferred. Furthermore, an anionic surfactant, an amphoteric surfactant, and an organic solvent such as alcohol can be added to the developer as required.

[Example 2 (Preparation of aluminum plate) An aluminum plate with a thickness of 0.24 mrA (material: 1050,
After degreasing H16) in a 5% by weight aqueous sodium hydroxide solution at 60°C for 1 minute, it was heated in a 0.5 molar hydrochloric acid aqueous solution of ]i at a temperature of 25°C and a current density of 60.
A/ (In', treatment time; electrolytic etching treatment was performed under the conditions of 30 seconds.Next, after performing a desmut treatment in a 5% by weight aqueous sodium hydroxide solution at 60°C for 10 seconds, 20wt'x, Temperature in 1aa solution: 20℃
The anodic oxidation treatment was performed under the following conditions: current density: 3 A/d1 = treatment time: 1 minute.

Furthermore, hot water sealing treatment was performed with hot water at 30°C for 20 seconds.
An aluminum plate as a support for lithographic printing plate material was produced.

Coating each photosensitive composition coating solution with the composition shown below on the aluminum plate prepared as above using a rotary coating machine,
Dry at 90°C for 4 minutes to obtain positive photosensitive lithographic printing plate sample N.
011 was obtained.

Photosensitive composition coating liquid composition/quinonediazide compound (QD-1) 2. OQ・
Vinyl resin of the present invention (polymer 1)5. OP・Novolac resin A of the present invention 1.0 Q・Victoria Pure Blue BOH (manufactured by Hodegaya Chemical ■) O, oag・
1,2-naphthoquinone-2-diazide 4-sulfonyl chloride 0. oeg methyl cellosolve
1001p and 1 to the above coating liquid composition.
Sample No. 1 except that the vinyl resin of the present invention, the novolak resin of the present invention, or 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and their addition m were changed as shown in Table 1. Positive-working photosensitive lithographic printing plate samples Nos. 2 to 7 were prepared in the same manner as above.

A step tablet for sensitivity measurement (Eastman
A 2KW metal halide lamp (Idol Fin 2000 manufactured by Iwasaki Electric Co., Ltd.) was closely attached to the Kodak II No. 2, 21-step gray scale with a density difference of 0.15
) was used as a light source and exposed under conditions of 8.0 mW/Cf. Next, this sample was developed at 27° C. for 20 seconds using a developer prepared by diluting 5DR-1 (manufactured by Konica ■) six times with water to obtain a lithographic printing plate sample.

In order to examine over-developability, a developer with excessive developing ability was prepared by diluting 5DR-1 5 times, and the exposed sample was developed at 27°C for 40 seconds, and the steps compared to standard development were carried out. Over-developability was determined based on the increase in the number of solid layers. The results are shown in Table 1. The smaller the increase in the number of solid steps, the better the over-development performance.

Further, the entire surface of the lithographic printing plate sample was gummed at 60°C.
After drying the gum for 10 minutes at °C, perform printing, and measure the number of sheets from the start of printing until ink is evenly applied to the image area (gum removability) and the number of sheets on which good prints can be obtained (printing durability).
The results were investigated for grain oil-based inks and UV inks, and the results are shown in Table 1.

Test conditions are shown below.

1 UV ink receptivity (gum removability) Nibrate gum liquid 5GU-3 (manufactured by Konica ■) was diluted twice and applied with a sponge, dried at 60℃ for 10 minutes, and the same as the printing durability (general ink) below. I printed it out and looked it up.

2 Printing Durability Printing was carried out on high-quality paper at 6000 sheets/hour using a Kani Heidel GT06000 stamp 8!1 machine. The general ink used was Mark Five Beni Ink (manufactured by Toyo Ink ■), and the UV ink was Toyo Flash Dry-〇L-Beni A.
P (manufactured by Toyo Ink Co., Ltd.).

When printing with UV ink, use Toyo Flash Drive Brate Cleaner (manufactured by Toyo Ink Co., Ltd.).
The plate surface was wiped at a rate of 1,500 times.

ll]; Vinyl d (fatty polymer) of the present invention (MW=22000. Mw/Mn=3.2m:n=
40:60) Tg=140'C Polymer 2 (M+n=20000. Mw/Mn=3.0m:n:
1=30240:30) y=150℃ Polymer 3 (Mw=35000. Mw/Mn=2,0a=:
n: N=ZO:50:20]T9=130"C Polymer 4 CH.

(Mw=25000. Mw/Mn=2.5m:n:
Z 30:35:35) Tg=]OO°C Polymer 5 +12: Novolak resin A of the present invention; ■ Copolycondensation resin of cresol, p-cresol, and formaldehyde (molar ratio of each of l-cresol and p-cresyl is 7) 3, lylw 000゜Mw /Mn TΩ -70℃ Copolycondensation resin of phenol, m-resol, p-cresyl, and formaldehyde (the molar ratio of each of phenol, ■-cresol, and p-cresol is 2゛2゜6.M
w -6,000, Mw /Mn -5,5>Tg-4
0°C below margin Knee Car 3; Kin/Nan anode compound QD-1 ○ QD-2 x:y=1:3 MV of resin before reacting with QD 4w=2000D-3 MV of resin before reacting with QD =2000O2 b.

+14; a: 1.2-naphthoquinone-2-diazide-4sulfonyl chloride b: 2.4-bis(trichloromethyl)-6-(4-methoxynaphthyl) -s -t-lyazine c: 2-1-lichloromethyl -5-(p-methoxystyryl)-1,3,4-oxadiazole d: 2-trichloromethyl-5-(β-benzofuryl vinyl) 1,3,4-oxadiazole e: 2-trichloromethyl -5-(ρ-butoxystyryl)-1,3,4-oxadiazole As is clear from Table 1, the test FI No of the present invention,
All of Samples Nos. 1 to 5 are superior to Comparative Samples No. 6 and 7 in terms of over-developability, UV ink receptivity, and printing durability.

[Effects of the Invention] As explained in detail above, the photosensitive composition of the present invention improves processing chemical resistance, processing chemical resistance, and
In particular, it is possible to provide a photosensitive lithographic printing plate that has excellent UV ink properties and excellent over-developability.

Claims (1)

[Claims] Quinonediazide compound, glass transition temperature (Tg) is 7
A photosensitive composition containing a vinyl resin having a value within the range of 0 to 200°C and a novolak resin having a glass transition temperature (Tg) within the range of 30 to 100°C.