JPH07333839A - Photosensitive planographic printing plate and photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. to obtain such a photosensitive planographic printing plate that can be developed with a developer of rather low pH as pH<12.5, gives excellent positive images with little change in the image forming property when the developing conditions vary, and has excellent printing performance and printing durability after burning treatment. CONSTITUTION:This photosensitive compsn. contains a polymer compd. having a partial structure expressed by the formula. The photosensitive planographic printing plate is obtd. by applying this photosensitive compsn. on a supporting body and dissolving and removing the photosensitive compsn. in the exposed part with an alkali soln., while using the photosensitive compsn. remaining on the unexposed area as an ink accepting part. In the formula, R1 is H, a halogen or alkyl group, each of R2 and R3 are H, a halogen, alkyl group, aromatic group, alkoxy group, and the like, and n is 2 or 3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a positive-working photosensitive lithographic printing plate and a photosensitive composition.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolac type phenolic resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate and as a photoresist. However, a photosensitive composition using a phenolic resin usually has to be developed with an alkaline aqueous solution having a high pH of 13 or more. However, such a high pH developer is safe to handle or is a waste treatment solution. It was by no means desirable for its suitability. In order to improve the drawbacks of these conventional phenol resins, Japanese Patent Publication No. 1-53451 proposes to use a polymer compound obtained by polymerizing a monomer of an acrylic acid derivative as a binder. Further, JP-A-3-68946 proposes to use as a binder a polymer compound obtained by polymerizing a monomer of an N-phenylacrylamide derivative having a carboxylic acid group in a photosensitive lithographic printing plate which does not require immersion. . Further, JP-A-50-55406 proposes to use a polymer compound obtained by polymerizing a monomer of an acrylamide derivative having a phenolic hydroxyl group as a binder. Further, in JP-A-51-36129, (hydroxyphenyl)
It has been proposed to use a polymer compound obtained by polymerizing a monomer of an acrylate derivative as a binder. Further, West German Patent No. 3528390 proposes to use a polymer compound obtained by polymerizing a monomer of a polyhydroxyphenyl acrylate derivative as a binder. Further, West German Patent No. 3528929 proposes to use, as a binder, a polymer compound obtained by polymerizing a monomer of an acrylic derivative containing a monohydroxyphenyl group and an alkylene linking chain.
Although it was possible to develop with an alkaline aqueous solution having a pH of 12.5 or less with any of the binders, the positive image was completely dissolved by the development, a very soft image was given, and the image was slightly changed due to a change in the developing condition. There was a problem that the formability varied greatly. US Pat. No. 4,72
No. 4,195 proposes to use a polymer compound obtained by copolymerizing a monomer of an acrylic derivative containing a phenolic hydroxyl group and a monomer containing a fluorine atom in a photosensitive lithographic printing plate not requiring immersion water. Has been done. Even if this binder was used, it was possible to develop with an alkaline developer having a pH of 12.5 or less, but at the time of printing, the adhesiveness of the ink in the image area, that is, the area where the photosensitive layer remains (hereinafter referred to as "inking performance"). ) Was bad. JP-A-63-226641 and Japanese Patent Application No. 5-170484 propose to use a polymer compound obtained by polymerizing a monomer of an N-sulfonyl (meth) acrylamide derivative or a sulfonimide derivative as a binder. . Further, Japanese Patent Application Nos. 5-183022 and 5-183023 propose a binder obtained by polymerizing a monomer of an N-phenylacrylamide derivative having a carboxyl group at the ortho position. Both of the binders were developable with an alkaline aqueous solution having a pH of 12.5 or less, and the change in the image forming property due to the change in the developing conditions was small, and a positive image with good inking property could be provided. These have a small difference in optical density between the exposed portion and the unexposed portion (hereinafter referred to as "printing out"). In addition, there is a problem that the printing durability after heating (hereinafter referred to as burning) after development is insufficient.

[0003]

Accordingly, the object of the present invention is to develop with an alkaline aqueous solution having a relatively low pH, and
A photosensitive lithographic printing plate and a photosensitive lithographic printing plate which give good positive images with little change in image formability due to changes in development conditions, have good printout performance, and good printing durability after burning treatment. It is to provide a photosensitive composition to give.

[0004]

As a result of intensive studies, the inventors of the present invention have invented a photosensitive lithographic printing plate useful for achieving the above object. That is, the present invention has a photosensitive composition containing a polymer compound having a partial structure represented by the following general formula [I] on a support, and the exposed portion of the photosensitive composition is dissolved in an alkaline aqueous solution. A photosensitive lithographic printing plate comprising a photosensitive composition which is an unexposed area where the photosensitive composition remains and which serves as an ink receiving area.

[0005]

[Chemical 8]

In the general formula [I], X is an alkylene group or a substituent
Alkylene group, -CH₂CH₂OCH ₂CH₂-,

[0007]

[Chemical 9]

Represents R ₁ represents a hydrogen atom, a halogen atom or an alkyl group. R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group, —OR ₄ , or —COO.
_{R 5, -CONHR 6, -COR 7} , or or represents -CN, or R ₂ and R ₃ may bond together to form a ring, each is R ₄ to R ₇ alkyl group or an aromatic group Represent.
n represents 2 or 3.

Further, they have invented a photosensitive composition useful for achieving the above object. That is, a photosensitive composition containing a polymer compound comprising a repeating unit represented by the following general formula [P], or a partial structure represented by the above general formula [I] and the following general formula [II] ] To [V] and a copolymer having at least one partial structure selected from the group consisting of [V] to [V] as a polymer compound.

[0010]

[Chemical 10]

In the general formula [P], X, R _{1 to} R ₇ and n
Are respectively synonymous with X, R _{1 to} R ₇ and n in the general formula [I], and p represents a positive integer.

[0012]

[Chemical 11]

In the general formula [II], R ₈ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). A represents a phenylene group or a substituted phenylene group.
The B -CO-, or -SO ₂ - represents a. E is -CO-
R _9, or an -SO ₂ -R _9. R ₉ represents an alkyl group, a substituted alkyl group, an aromatic group or a substituted aromatic group. m and n represent 0 or 1, but m and n are not 0 at the same time.

[0014]

[Chemical 12]

In the general formula [III], R ₁₀ represents a hydrogen atom, a halogen atom or an alkyl group, Y represents an oxygen atom,
-NH-, or -N (R ₁₅₎ - (wherein R ₁₅ represents an alkyl group) _{represents, R 11, R 12, R} 13, and R _14,
Each independently, a hydrogen atom, a halogen atom, an alkyl group,
Substituted alkyl group, aryl group, substituted aryl group, -OR
_{16, -OCO-R 17, -NHCO} -R 18, -NHCON
HR ₁₉ , -OCONH-R ₂₀ , -COOR ₂₁ , -CON
HR ₂₂ , -COR ₂₃ , -CONR ₂₄ R ₂₅ , -CN, or -CHO group is represented, or two of R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are bonded to each other to form a ring. Alternatively, R _{16 to} R ₂₅ each represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. However, R ₁₁ ,
At least one of R ₁₂ , R ₁₃ and R ₁₄ represents a group other than a hydrogen atom.

[0016]

[Chemical 13]

In the general formula [IV], R ₂₆ represents a hydrogen atom, a halogen atom or an alkyl group, and R ₂₇ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic group or a substituted aromatic group,
Alternatively, it represents an aralkyl group. Z is an oxygen atom or -NH
Represents-.

[0018]

[Chemical 14]

In the general formula [V], R ₂₈ represents a hydrogen atom, a halogen atom or an alkyl group, R ₂₉ represents an aromatic group,
Represents -CN or -CHO.

It is just surprising that the above polymer compound gives a photosensitive composition which can be developed with a developer having a pH of 12.5 or less and has a wide range of appropriate developing conditions (wide development latitude). there were. Moreover, it has excellent bake-out performance,
It was also surprising that the printing durability after burning was excellent.

In the above general formula [I], R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms. Particularly preferred is a hydrogen atom or a methyl group. X is an alkylene group, a substituted alkylene group,
_{-CH 2 CH 2 OCH 2 CH 2} -,

[0022]

[Chemical 15]

Is preferably an alkylene group having 1 to 20 carbon atoms or a substituted alkylene group, and particularly preferably an alkylene group having 2 to 6 carbon atoms. As the substituent of the substituted alkylene group, a hydroxyl group and a carbon number of 1 to 1
An alkyl group having 0 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an acyloxy group having 1 to 10 carbon atoms is preferable. R
₂ and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group,
It represents OR ₄ , —COOR ₅ , —CONHR ₆ , —COR ₇ , or —CN, or R ₂ and R ₃ may combine to form a ring. Here, R _{4 to} R ₇ each represent an alkyl group or an aromatic group. More preferable R ₂ and R ₃ are each independently a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, —OR ₄ , —COOR ₅ , or —CONHR.
₆ , —COR ₇ and —CN, where R _{4 to} R ₇ are an alkyl group having 1 to 4 carbon atoms or a phenyl group. Particularly preferred R ₂ and R ₃ are each independently a hydrogen atom, a chlorine atom, a methyl group or a methoxy group.

In the above general formula [II], R ₈ is a hydrogen atom, a halogen atom or an alkyl group (preferably having a carbon number of 1 to 4), more preferably a hydrogen atom or a methyl group. A is a phenylene group or a substituted phenylene group, more preferably a phenylene group or m = 0. The preferred alkyl group represented by R ₉ is a chain, branched or cyclic alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl and cyclohexyl, and the substituted alkyl group is as described above. Chlorine, bromine, or other halogen atom in the unsubstituted alkyl group,
Examples thereof include those substituted with a substituent such as an aryl group such as phenyl, an amide group such as acetamide, an alkoxy group such as methoxy and butyloxy, and an alkoxycarbonyl group such as ethoxycarbonyl. See also R ₉
As a preferred aromatic group represented by, in addition to an aryl group (carbocyclic aromatic group) such as phenyl, naphthyl and anthranyl, a heterocyclic aromatic group such as benzofuryl can be preferably used. Preferred substituents of the substituted aromatic group represented by R ₉ are halogen atoms such as chlorine and bromine, alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl and butyl, and 1 to 10 carbon atoms such as methoxy and butyloxy. Examples thereof include an alkoxy group, an amide group such as acetamide, and an aryl group such as phenyl.

In the above general formula [III], R ₁₀ represents a hydrogen atom, a halogen atom or an alkyl group. The halogen atom is preferably chlorine or bromine atom. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
Individual ones can be used. In the above formula, R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Substituted aryl _{group, -OR 16, -OCO-R 17} , -NHC
_{O-R 18, -NHCONHR 19,} -OCONH-R 20,
-COOR ₂₁ , -CONHR ₂₂ , -COR ₂₃ , -CON
R ₂₄ R _25, represents a -CN or -CHO group,. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. The aromatic group has 6 to 2 carbon atoms such as phenyl and naphthyl.
0 is used, and more preferably 6 to 10 are used. Examples of the substituent of the substituted alkyl group and the substituted aromatic group include an aromatic group, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group, an acyloxy group, a formyl group and an aryloxy group. . Further, examples of the substituent of the substituted aromatic group include an alkyl group having 1 to 10 carbon atoms in addition to the above-mentioned ones.

Two of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may combine with each other to form a ring. The ring formed by combining two members out of R _{11 to} R ₁₄ is preferably a 5- to 7-membered ring, and cyclopentane, cyclohexane, benzene,
Examples thereof include an aliphatic ring having 4 to 14 carbon atoms such as naphthalene, an aryl ring, and a hetero ring having 1 to 4 hetero atoms such as pyridyl, furyl, pyrrole and indole. R ₁₅ may be an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R _{16 to} R ₂₅ represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. The aryl group has 6 to 2 carbon atoms such as phenyl and naphthyl.
0 is used, and more preferably 6 to 10 are used. As the substituent of the substituted alkyl group and the substituted aryl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 10 carbon atoms, and 1 carbon atom -10
Individual acyloxy groups, formyl groups and the like. As the substituent of the substituted aromatic group, in addition to the above-mentioned ones, an alkyl group having 1 to 10 carbon atoms can be mentioned. In the above formula, R ₁₀ is preferably a hydrogen atom or a methyl group, and Y is preferably —NH—. R _{11 to} R ₁₄ are halogen atoms, 1 to 8
An alkyl group having 4 carbon atoms; an alkyl group having a total of 1 to 15 carbon atoms substituted with a halogen atom, an aryl group or an alkoxy group; -OR ₁₆ group; -OCOR ₁₇ group;
NHR ₂₀ group (wherein R ₁₆ , R ₁₇ , and R ₂₀ are each independently an alkyl group having 1 to 8 carbon atoms; an aryl group; a total number of carbon atoms 1 substituted with a halogen atom, an aryl group, or an alkoxy group) From 15 to 15 substituted alkyl groups; or a substituted aryl group having a total of 6 to 15 carbon atoms substituted with a halogen atom, an alkyl group or an alkoxy group is preferred), and R _{11 to} R ₁₄ are 2 of them. It is also preferred that the are bonded to each other to form a ring. Specific examples of the preferable ring include naphthalene, tetralin, indene, indanone, tetralone, benzofuran, and indole, in the condensed form with the aryl group to which a carboxyl group is bonded.

In the above formula [IV], R ₂₆ represents a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. R ₂₇ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group or an aralkyl group, preferably a hydrogen atom, a chain having 1 to 15 carbon atoms, a branched chain, or a ring. Alkyl group or substituted alkyl group having 6 to 15 carbon atoms
Aromatic groups or substituted aromatic groups, and aralkyl groups having 7 to 12 carbon atoms. Here, as the substituent, a hydroxy group, an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), a phenoxy group, a chlorine atom, -CN, -S.
Examples include O ₂ NH ₂ and epoxy groups.

In the above general formula [V], R ₂₈ represents a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. R ₂₉ represents an aromatic group, —CN or —CHO, more preferably a phenyl group or —CN.

Specific examples of the monomer capable of deriving the partial structure represented by the above general formulas [I] to [V] are shown below. However, the present invention is not limited to this specific example. (Specific examples of the monomer capable of deriving the partial structure represented by the general formula [I])

[0030]

[Chemical 16]

[0031]

[Chemical 17]

(Specific examples of the monomer capable of deriving the partial structure represented by the general formula [II])

[0033]

[Chemical 18]

(Specific examples of the monomer capable of deriving the partial structure represented by the general formula [III])

[0035]

[Chemical 19]

(Specific examples of the monomer capable of deriving the partial structure represented by the general formula [IV]) Acrylic acid, methyl acrylate, ethyl acrylate, iso-butyl acrylate, n-butyl acrylate, hexyl acrylate, Acrylic acid and its esters such as octyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate; or methacrylic acid, methyl methacrylate, ethyl methacrylate , N-butyl methacrylate, iso-butyl methacrylate, te methacrylate
rt-Butyl, hexyl methacrylate, methacrylic acid-2
-Ethylhexyl, lauryl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid and its esters such as tetrahydrofurfuryl and allyl methacrylate; or acrylamide, N-
Methyl acrylamide, N-ethyl acrylamide, N
-Isopropyl acrylamide, Nt-butyl acrylamide, N-phenyl acrylamide, N-benzyl acrylamide, or acrylamides represented by the following chemical formula 20;

[0037]

[Chemical 20]

Alternatively, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, Nt-butylmethacrylamide, Nn-octylmethacrylamide, N-
(2-Ethylhexyl) methacrylamide, N- (2-
Hydroxypropyl) methacrylamide, N-benzylmethacrylamide, or methacrylamides represented by the following Chemical Formula 21.

[0039]

[Chemical 21]

(Specific examples of the monomer capable of deriving the partial structure represented by the general formula [V]) Acrylonitrile, acrolein, or styrene.

Next, typical examples of the polymer compound according to the present invention are shown below. However, the composition ratio of the polymer structure is a molar percentage.

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

The polymer compound according to the present invention can be generally produced by a radical chain polymerization method ("Textbook of Polymer Science" 3rd ed, (1984) F.
See W. Billmeyer, A Wiley-Interscience Publication). The molecular weight of the polymer compound having the partial structure represented by the general formula [I] may be in a wide range, but when measured by gel permeation chromatography or light scattering method using polystyrene as a standard, the weight average molecular weight ( The Mw) is preferably in the range of 500 to 2,000,000, more preferably 2,000 to 1,000,000.

As the positive-working photosensitive compound used in the present invention, an o-naphthoquinonediazide compound is preferable, and 1,2-diazonaphthoquinonesulfonic acid chloride described in JP-A-43-28403 is used. And an ester of pyrogallol-acetone resin or an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and 2,3,4-trihydroxybenzophenone are preferable.

Other suitable orthoquinonediazide compounds are described in US Pat. Nos. 3,046,120 and 3,188,210.
There is an ester of 2-diazonaphthoquinone sulfonic acid chloride with a phenol-formaldehyde resin. Other useful o-naphthoquinonediazide compounds are described and known in numerous patent publications. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, Japanese Patent Publication No. 41-11222, Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 49-17481, and U.S. Pat. No. 2,797,21.
No. 3, No. 3,454,400, No. 3,544,3
No. 23, No. 3,573,917, No. 3,674,
No. 495, No. 3,785,825, US Pat.
227,602, 1,251,345, 1,267,005, 1,329,888, 1,330,932, German Patent 854,890.
The items described in each specification such as No. can be mentioned.

Further, as a photosensitive compound or a photosensitive mixture acting as a positive type without using an o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696. Can also be used in the present invention. Furthermore, a compound that generates an acid by photolysis and C that dissociates by the acid
A photosensitive mixture with a compound having a —O—C group or a C—O—Si group can also be used in the present invention. For example, a compound that generates an acid by photolysis and acetal or O, N
-Combination with acetal compound (JP-A-48-8900)
3), a combination with an orthoester or amide acetal compound (JP-A-51-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), an enol ether compound. Combination (JP-A-55-12995) and a combination with N-acyliminocarbonate (JP-A-55-12623).
No. 6), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a silyl ester compound (JP-A-60-10247) and a combination with a silyl ether compound (special Kaisho 60-3754
No. 9, JP-A-60-12146) and the like. The amount of the positive-working photosensitive compound or photosensitive mixture in the photosensitive composition of the present invention is 5 to 80.
%, More preferably 10 to 50% by weight.

In the composition of the present invention, in addition to the polymer of the present invention, known alkali-soluble polymers such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. A compound can be included. The alkali-soluble polymer compound is used in an amount of 0 to 200% by weight, preferably 0 to 100% by weight, based on the polymer having the partial structure represented by the general formula [I]. In the composition of the present invention, a cyclic acid anhydride may be added to enhance the sensitivity, a printout agent for obtaining a visible image immediately after exposure, a dye or other filler as an image colorant may be added. As the cyclic acid anhydride, there are U.S. Pat. No. 4,115,12.
No. 8, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
There are 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like.

By containing 1 to 15% by weight of these cyclic acid anhydrides in the total composition, the sensitivity can be increased up to about 3 times. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically, JP-A-50-3620
9 and JP-A-53-8128, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-3622.
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A No. 3 and JP-A No. 54-74728 can be mentioned. In addition to the salt-forming organic dyes described above, other dyes can be used as the image colorant. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 102, Oil Green BG, Oil Blue B
OS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-506 (above,
Orient Chemical Industry Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI4)
2535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015) and the like.

Various additives can be added to the photosensitive composition of the present invention. For example, alkyl ethers (for example, ethyl cellulose and methyl cellulose) and fluorine-based surfactants (for example, those described in JP-A-62-170950 are preferable) for improving coatability.
And nonionic surfactants (particularly fluorine-based surfactants are preferable), thermal crosslinking agents for increasing printing durability after burning treatment (for example, compounds described in JP-B-1-49932, European Patent EP589309A1). , Japanese Patent Application 4-
No. 303515 and No. 5-161256), a plasticizer for imparting flexibility and abrasion resistance to the coating film (eg, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, Dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid oligomers and polymers (tricle phosphate is particularly preferable among these)], and a feeling for improving the image area oil sensitivity Fatting agents (for example, JP-A-55-5
Half-esterified products of styrene-maleic anhydride copolymer with alcohol, octylphenol formaldehyde novolac resin, 50% fatty acid esterified product of p-hydroxystyrene, and the like) described in JP-A No. 27) are preferably used. The amount of these additives to be added is
Depending on the purpose, it is generally 0.
It is from 01 to 30% by weight.

The composition of the present invention is dissolved in a solvent which dissolves each of the above components and applied on a support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, toluene, There are ethyl acetate and the like, and these solvents are used alone or as a mixture. The concentration (solid content) in the above components is 2 to 50% by weight.
Is. Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate, it is generally preferable that the solid content is 0.5 to 3.0 g / m ² . As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

The photosensitive composition of the present invention is particularly suitable as a photosensitive layer of a photosensitive lithographic printing plate. Hereinafter, aspects of the photosensitive lithographic printing plate will be described in detail. The support used in the present invention is preferably a dimensionally stable plate.
Such dimensionally stable plate-like materials include those conventionally used as a support for printed matter, and they can be preferably used in the present invention. As such a support,
Paper, paper laminated with plastics (eg polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, cellulose diacetate, cellulose triacetate,
Cellulose propionate, cellulose butyrate, acetic acid-cellulose butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene,
Examples include plastic films such as polycarbonate and polyvinyl acetal, and papers or plastic films laminated or vapor-deposited with the above metals. Of these supports, the aluminum plate is preferred because it is dimensionally remarkably stable, is inexpensive, and has particularly good adhesion to the photosensitive layer of the present invention.
Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a metal, particularly an aluminum support, it is desirable that surface treatment such as graining treatment and anodic oxidation treatment be performed. Further, in order to increase the hydrophilicity of the surface, dipping treatment may be performed in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like. As described in U.S. Pat. No. 2,714,066, an aluminum plate which has been grained and then immersed in an aqueous sodium silicate solution, as described in Japanese Patent Publication No. 47-5125. It is preferable that after the anodic oxidation treatment, the product is immersed in an aqueous solution of an alkali metal silicate. Also, U.S. Pat. No. 3,658,662
The silicate electrodeposition as described in the specification is also effective. Further, a surface obtained by combining the electrolytic grain as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503 with the above anodizing treatment and sodium silicate treatment. Processing is also useful. Further, as disclosed in JP-A-56-28893, a brush grain, an electrolytic grain, an anodic oxidation treatment, and a sodium silicate treatment which are sequentially performed are also preferable.

[Organic Undercoat Layer] The aluminum plate is optionally provided with an organic undercoat layer before coating the photosensitive layer.
Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid esters, optionally substituted phenylphosphinic acids, naphthylphosphinic acids, alkylphosphinic acids and other organic phosphinic acids such as glycerophosphinic acid, glycine and β
Selected from amino acids such as alanine, and hydrochlorides of amines having a hydroxyl group such as triethanolamine hydrochloride, but two or more kinds may be mixed.

This organic undercoat layer can be provided by the following method. That is, water or a solvent in which the above organic compound is dissolved in an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof is applied on an aluminum plate and dried to provide a method, and water or methanol, ethanol, methyl ethyl ketone, etc. In a solution prepared by dissolving the organic compound in an organic solvent or a mixed solvent thereof, an aluminum plate is immersed to adsorb the organic compound, and then washed with water or the like and dried to form an organic undercoat layer. Is. In the former method,
A solution having a concentration of 0.005 to 10% by weight of the above organic compound can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5%.
% By weight, the immersion temperature is 20 to 90 ° C., preferably 2
It is 5 to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The pH of the solution used for this purpose can be adjusted with a basic substance such as ammonia, triethylamine, potassium hydroxide, etc., or an acidic substance such as hydrochloric acid, phosphoric acid, etc., and it can also be used in the range of pH 1-12. Also,
A yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate.

The coating amount of the organic undercoat layer after drying is 2 to 20.
0 mg / m ² are suitable, and preferably from 5 to 100 mg / m ^2. If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same applies when the amount is larger than 200 mg / m ² . The surface of the photosensitive layer of the photosensitive lithographic printing plate shortens the evacuation time during contact exposure using a vacuum baking frame,
Moreover, in order to prevent burning blur, it is preferable to form a mat.
Specifically, JP-A-50-125805 and JP-B-5757
No. 6582, No. 61-28986, a method for providing a mat layer as described in JP-B No. 62-6.
There is a method of heat-bonding a solid powder as described in Japanese Patent No. 2337.

The light source used for image exposure of the photosensitive lithographic printing plate of the present invention includes carbon arc lamp, mercury lamp, xenon lamp, tungsten lamp, metal halide lamp and the like. As a developing solution for the photosensitive lithographic printing plate of the present invention, an alkaline aqueous solution having a pH of 12.5 or less can be used, and more preferably an alkaline aqueous solution having a pH of 10.5 to 12.5 is used. Examples of the basic compound used for adjusting the pH value include sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic, sodium phosphate dibasic, potassium phosphate dibasic, and potassium phosphate dibasic. Phosphates such as ammonium phosphate, ammonium hydrogen carbonate,
Carbonates such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, borates such as sodium borate, potassium borate and ammonium borate, and potassium hydroxide, sodium hydroxide, lithium hydroxide. Examples thereof include alkali metal hydroxides and ammonium hydroxide. Particularly preferred is a combination of carbonate and hydrogen carbonate. These may be used alone or as a mixture.

As another basic compound, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine,
Triethanolamine, monoisopropanolamine,
Water-soluble organic amine compounds such as diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like can be mentioned. Of these, especially monoethanolamine,
Diethanolamine, triethanolamine and the like are preferable, and they may be used in combination with an inorganic alkali metal salt or the like. The concentration of these basic compounds in the aqueous solution is pH 12.5 or less as described above, more preferably pH 10.5 to
It is used in the range of 12.5, but generally it can be selected from the range of 0.05 to 10% by weight.

If necessary, an anionic surfactant may be added to the developing solution. Furthermore, an organic solvent can be added. As the anionic surfactant, for example,
Lauryl alcohol sulphate sodium salt, octyl alcohol sulphate sodium salt, lauryl alcohol sulphate ammonium salt, secondary sodium alkyl sulphate and other higher alcohol sulfuric acid ester salts having 8 to 22 carbon atoms, for example cetyl alcohol phosphate sodium salt Alkylaryl sulfonates such as aliphatic alcohol phosphate salts such as sodium salt of dodecylbenzene sulfonic acid, sodium salt of isopropylnaphthalene sulfonic acid, sodium salt of metanitrobenzene sulfonic acid such as C ₁₇ H ₃₃ CON ( Sulfonates of alkylamides such as CH ₃ ) CH ₂ CH ₂ SO ₃ Na, etc., such as sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester Included are sulfonates of dibasic fatty acid esters such as tell.

It is appropriate that the anionic surfactant is contained in the range of 0.1 to 5% by weight based on the total weight of the developing solution at the time of use. When it is less than 0.1% by weight, its use effect is low, and when it is more than 5% by weight,
Problems such as excessive elution (color loss) of the dye in the image area and deterioration of mechanical and chemical strength such as abrasion resistance of the image will occur. As the organic solvent, those having a solubility in water of 10% by weight or less are suitable, and those having a solubility of 5% by weight or less are preferable. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol-1, 4-phenylbutanol-1, 4-phenylbutanol-2, 2-phenylbutanol-1, 2,
-Phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol,
Examples thereof include benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol and 3-methylcyclohexanol.

The content of the organic solvent is preferably 1 to 5% by weight based on the total weight of the developing solution at the time of use. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the anionic surfactant as the amount of the organic solvent increases. This is because the amount of anionic surfactant is small,
This is because if a large amount of the organic solvent is used, the organic solvent will not dissolve, and it will be impossible to expect to secure good developability.
Further, if necessary, additives such as a defoaming agent and a water softener can be contained. As a water softener, for example, Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO
Polyphosphates such as ₃ Na ₂ and Calgon (sodium polymetaphosphate), such as ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt , Its sodium salt; hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3 -Aminopolycarboxylic acids such as diamino-2-propanoltetraacetic acid, its potassium salt, its sodium salt, etc., 2-phosphonbutanetricarboxylic acid-1,2,4, its potassium salt, its sodium salt; 2-phos Hombutyne tricarboxylic acid-2,
3,4, its potassium salt, its sodium salt; 1-phosphonoethanetricarboxylic acid-1,2,2, its potassium salt, its sodium salt; 1-hydroxyethane-1,1
-Diphosphonic acid, its potassium salt, its sodium salt;
Aminotri (methylenephosphonic acid), its potassium salt,
Mention may be made of organic phosphonic acids such as their sodium salts. The optimum amount of such a water softening agent varies depending on the hardness of the hard water used and the amount of the hard water used.
It is contained in an amount of 01 to 5% by weight, more preferably 0.01 to 0.5% by weight.

The photosensitive lithographic printing plate of the present invention is described in JP-A-54 / 54.
No. 8002, No. 55-115045, JP-A-59-
It goes without saying that plate-making processing may be carried out by the method described in each publication of No. 58431. That is, after development processing,
After washing with water, desensitization treatment, desensitization treatment as it is, treatment with an aqueous solution containing an acid, or desensitization treatment after treatment with an aqueous solution containing an acid may be performed. Further, in the developing step of this type of photosensitive lithographic printing plate, the developing solution becomes fatigued depending on the amount of treatment, and therefore the replenishing solution or a fresh developing solution may be used to recover the processing ability. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246.

Further, the plate making process as described above is described in Japanese Patent Application Laid-Open No.
It is preferably carried out by an automatic developing machine as described in Nos. -7054 and 2-32357. Further, when the photosensitive lithographic printing plate of the present invention is imagewise exposed, developed, washed with water or rinsed and then the unnecessary image portion is erased, it is described in JP-B-2-13293. It is preferable to use such an erasing liquid. Further, as the desensitizing gum which is optionally applied in the final step of the plate making process, JP-B-62-16834, JP-B-62-25118,
JP-B-63-52600, JP-A-62-7595,
Those described in JP-A-62-11693 and JP-A-62-83194 are preferable. Furthermore,
When the photosensitive lithographic printing plate of the present invention is imagewise exposed, developed, washed with water or rinsed, erased if desired, and burned after washing with water, the Japanese Patent Publication No. SHO 61 is used before burning.
-2518, JP-B-55-28062, JP-A-62.
-31859 and JP-A-61-159655, it is preferable to treat with a leveling solution.

[0066]

EXAMPLES The present invention will be described in more detail with reference to synthetic examples and examples, but the contents of the present invention are not limited thereto. All percentages are by weight unless otherwise specified.

[Synthesis Example 1] 2- (2,4-dihydroxybenzoyloxy) ethyl
Synthesis of Acrylate (Compound of Example 1) This compound was synthesized by the following scheme.

[0068]

[Chemical formula 26]

1) Synthesis of 2-hydroxyethyl 2,4-dihydroxybenzoate (Compound a) 228.5 g (1.48 mol) of 2,4-dihydroxybenzoic acid and 500 ml of acetonitrile were placed in a 3-liter three-necked flask. Next, under water cooling, while maintaining the temperature at 60 ° C or lower, under stirring, 1,8-diazabicyclo-
[5.4.0] -7-undecene 248.3 g (1.6
3 mol) and 500 ml of acetonitrile were added dropwise. After the dropping, further, under the temperature condition of 60 ° C. or less,
A mixed solution of 222 g (1.78 mol) of bromoethanol and 300 ml of acetonitrile was added dropwise. After completion of dropping, 1
The mixture was heated under reflux for 0 hours. After allowing to cool, the reaction solution was poured into a beaker containing ethyl acetate and ice, and diluted sulfuric acid was added to neutralize the reaction solution. The reaction solution was transferred to a separating funnel, and the organic layer was washed twice with saturated saline. The organic layer was dried over magnesium sulfate and then suction filtered. While adding toluene to the filtrate, the solvent was distilled off under reduced pressure to precipitate crystals. The crystals were collected by filtration and dried to obtain 252 g of pale yellow crystals having a melting point of 136 to 138 ° C. (Yield 86%) The crystal structure was identified by the following NMR spectrum and elemental analysis values. ¹ H-NMR (δ: DMSO-d ₆ ) 3.68 (t, J = 4.9Hz, 2H), 4.27 (t, J = 4.9Hz, 2H), 4.94
(s, 1H), 6.29 (d, J = 2.0Hz, 1H), 6.38 (dd, J = 8.5, 2.0
Hz, 1H), 7.71 (d, J = 8.5Hz, 1H), 10.46 (s, 1H), 10.74
(s, 1H) Elemental analysis value C: 54.31%, H: 5.13%

2) Synthesis of 2- (2,4-dihydroxybenzoyloxy) ethyl acrylate (Specific Example 1) 2-hydroxyethyl was added to a 2 liter three neck flask.
2,4-Dihydroxybenzoate (Compound a) 139
g (0.7 mol), N-methylpyrrolidone 347 g
(3.5 mol) and 800 ml of acetonitrile were added. Next, by cooling with water as necessary, the temperature is raised to 40 ° C.
Acrylic chloride 190.1 with stirring while maintaining
A mixed solution of g (2.1 mol) and 200 ml of acetonitrile was added dropwise. After finishing the dropping, keep the reaction temperature at about 40 ° C,
It was stirred for 16 hours. After completion of the reaction, the reaction solution was poured into a beaker containing 1 g of 4-tert-butylpyrocatechol, ethyl acetate, ice and dilute sulfuric acid, and the organic layer was washed with saturated saline three times. The organic layer was dried over magnesium sulfate and then suction filtered. Crystals were precipitated by distilling off the solvent under reduced pressure while adding toluene to the filtrate. The crystals are collected by filtration and dried to give white crystals having a melting point of 120 to 120.5 ° C 1
67 g was obtained. (Yield 95%) The crystal structure is NM
It was identified from the R spectrum and the elemental analysis value. ¹ H-NMR (δ: DMSO-d ₆ ) 4.42 to 4.53 (m, 4H), 5.96 (d, J = 10.2Hz, 1H), 6.20 (dd,
J = 17.3, 10.2Hz, 1H), 6.27 ~ 6.40 (m, 4H), 7.61 (d, J
= 8.8Hz, 1H), 10.50 (s, 1H), 10.60 (s, 1H) Elemental analysis value C: 57.03%, H: 4.86%

[Synthesis Example 2] 2- (2,4-dihydroxybenzoyloxy) ethyl
Synthesis of Methacrylate (Compound of Example 2) In a 1-liter three-necked flask, 2-hydroxyethyl 2,4-dihydroxybenzoate (Compound a) 5 was added.
9.5 g (0.3 mol), N-methylpyrrolidone 149
g (1.5 mol) and 300 ml of acetonitrile were added.
Next, under ice-cooling, a mixed solution of 94.1 g (0.9 mol) of methacrylic acid chloride and 120 ml of acetonitrile was added dropwise with stirring while maintaining the temperature at 40 ° C. or lower. After completion of dropping, the mixture was stirred for 12 hours while maintaining the reaction temperature at 40 to 45 ° C.
After completion of the reaction, by post-treatment in the same manner as in Synthesis Example 1,
67 g of white crystals having a melting point of 115.5 to 116 ° C. were obtained.
(Yield 84%) The crystal structure was identified by the following NMR spectrum and elemental analysis values. ¹ H-NMR (δ: DMSO-d ₆ ) 1.86 (s, 3H), 4.40 to 4.55 (m, 4H), 5.69 (s, 1H), 6.03
(s, 1H), 6.30 (s, 1H), 6.38 (d, J = 8.8Hz, 1H), 7.62
(d, J = 8.8Hz, 1H), 10.50 (s, 1H), 10.60 (s, 1H) Elemental analysis value C: 58.51%, H: 5.33%

Synthesis Example 3 Synthesis of 2- (2,4,6-trihydroxybenzoyloxy) ethyl acrylate (Compound of Specific Example 3) This compound was synthesized by the following scheme.

[0073]

[Chemical 27]

1) 2-hydroxyethyl 2,4,6-
Synthesis of Trihydroxybenzoate (Compound b) A 500 ml three-necked flask was charged with 50.35 g (0.27 mol) of 2,4,6-trihydroxybenzoic acid monohydrate and 150 ml of acetonitrile. 50 ℃
1,8-diazabicyclo [5.4.
0] 7-Undecene (45.2 g, 0.30 mol) was added dropwise. After completion of the dropping, further under the temperature condition of 50 ° C. or less,
A mixed solvent of 40.8 g (0.33 mol) of bromoethanol and 100 ml of acetonitrile was added dropwise. After dropping 1
The mixture was heated under reflux for 6 hours. After completion of the reaction, post-treatment was carried out in the same manner as in Synthesis Example 1 to obtain 21.5 g of pale yellow crystals having a melting point of 130.5 to 133 ° C. (Yield 37.5%) The crystal structure was identified by the following NMR spectrum and elemental analysis values. ¹ H-NMR (δ: DMSO-d ₆ ) 3.68 (t, J = 5.0 Hz, 2H), 4.33 (t, J = 5.0 Hz, 2H), 5.84
(s, 2H), 10.23 (s, 3H) Elemental analysis value C: 50.21%, H: 4.69%

2) Synthesis of 2- (2,4,6-trihydroxybenzoyloxy) ethyl acrylate (compound of Example 3) 2-hydroxyethyl was added to a 300 ml three-necked flask.
2,4,6-Trihydroxybenzoate (Compound b)
21.3 g (99 mmol), N-methylpyrrolidone 4
5.5 g (460 mmol), 130 m of acetonitrile
l, 24.9 g (276 mmol) of acrylic acid chloride
Was added. Next, the mixture was stirred for 6 hours while maintaining the temperature at 40 ° C. After completion of the reaction, by post-treatment in the same manner as in Synthesis Example 1, white crystals 12.2 having a melting point of 108.5 to 110.5 ° C.
g was obtained. (Yield 45.9%) The crystal structure was identified by the following NMR spectrum and elemental analysis values. ¹ H-NMR (δ: DMSO-d ₆ ) 4.35 to 4.55 (m, 4H), 5.83 (s, 2H), 5.96 (d, J = 10.2Hz,
1H), 6.18 (dd, J = 17.2, 10.2Hz, 1H), 6.34 (d, J = 17.2H
z, 1H), 10.20 (s, 1H), 10.28 (s, 2H) Elemental analysis value C: 53.71%, H: 4.53%

Synthesis Example 4 Synthesis of Polymer No. 1 2- (2,4-dihydroxybenzoyloxy) ethyl
60 g of the acrylate (the compound of Example 1) and 120 g of N, N-dimethylformamide were placed in a 500 ml three-necked flask and kept at 65 ° C. with stirring under a nitrogen stream.
62.3 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was added. After 2 hours, 156 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was further added. After 2 hours, 156 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was added. After stirring for another 2 hours, the mixture was cooled to room temperature. Acetone 50 in the reaction solution
After adding ml, the mixture was poured into 2.1 liter of water with stirring.
The precipitated solid was collected by filtration and dried. According to the light scattering method, this solid was a polymer compound having a weight average molecular weight of 230,000. Yield 56g.

[Synthesis Examples 5 to 15] In the same manner as in Synthesis Example 4, various polymer compounds shown below were synthesized. However, the composition ratio in the polymer structure is a molar percentage. Polymer No. 1 synthesized in Synthesis Example 4 is also shown below.

[0078]

[Chemical 28]

[0079]

[Chemical 29]

[0080]

[Chemical 30]

[0081]

[Chemical 31]

Examples 1 to 3 An aluminum plate having a thickness of 0.30 mm and a nylon brush 4 were used.
The surface was grained using a water suspension of 00 mesh pumice and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C for 60 seconds for etching,
It was washed with running water, neutralized and washed with 20% HNO ₃ . This was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution under the condition of V _A = 12.7 V in an aqueous 1% nitric acid solution at an anodic electricity of 160 clones / dm ² . The surface roughness was measured to be 0.6 μm ( _Ra indication), followed by immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, followed by 20% H ₂ SO ₄ Current density 2 A / dm in aqueous solution
² was anodized to a thickness of 2.7 g / m ² . Then, it was immersed in a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water, and dried. The undercoat liquid (A) having the following composition is applied to the surface of the substrate thus treated
C. and dried for 30 seconds. The coating amount after drying was 30 mg / m ² .

Undercoating liquid (A) Phenylphosphonic acid 0.10 g Methanol 40 g Pure water 60 g A substrate (I) was prepared in this manner. Next, the following photosensitive solution (A) is applied onto this substrate (I) by rod coating.
A positive photosensitive lithographic printing plate was obtained by applying 5 ml / m ^{2 and} drying at 100 ° C. for 1 minute. The applied amount after drying is about 1.7 g / m ^2.
Met. Photosensitive liquid (A) 1,2-naphthoquinonediazide-5-sulfonyl chloride esterification reaction product of 2,3,4-trihydroxybenzophenone 0.75 g Polymer described in Table 1 2.0 g 2- (p -Butoxyphenyl) -4,6-bis (trichloromethyl-s-triazine) 0.02g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.03g crystal violet 0.01g oil blue # 603 (Orient Chemical Industries Ltd.) Made by company) 0.015 g ethylene dichloride 18 g 2-methoxyethyl acetate 12 g

Each of these photosensitive lithographic printing plates was 2K.
It was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a W metal halide lamp. The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, first, a developing solution (pH 1) prepared by diluting the following developing stock solution-1 with water to a stablon 900NP automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
0) and Finisher FP-2 manufactured by Fuji Photo Film Co., Ltd.
Were charged, and development processing was performed under the conditions of a developing solution temperature of 30 ° C. and a developing time of 12 seconds.

Stock solution for development-1 Sodium carbonate monohydrate 6 g Sodium hydrogencarbonate 3 g Ethylenediaminetetraacetic acid 2 g Sodium dodecylbenzenesulfonate 1 g Water 100 g

After development, it was checked whether an image could be obtained. If the photosensitive film could not be developed and remained as it was, the image forming property was evaluated as x (development failure), and if the photosensitive film was completely dissolved and not left, it was evaluated as x (overdevelopment) and a positive image was obtained. The image forming property was evaluated as ◯. Also ○ and ×
The middle of is indicated by △. In addition, in order to examine the range of suitable developing conditions (development acceptability), the change in tone reproducibility when immersed in the above developing solution for 2 minutes and developed and then immersed for 12 seconds and developed was examined. Those with almost no change are indicated with a circle, those with a large change are indicated with a cross, and the middle thereof is indicated with a triangle. Regarding the print-out property after exposure, the optical densities of the exposed and unexposed areas were measured using a Macbeth reflection densitometer. The image obtained by exposure is the optical density of the exposed area,
The larger the difference (ΔD) from that of the unexposed portion, the clearer the image. Further, the printing durability after the burning treatment was evaluated by the following method. After development, the plate surface was wiped with a burning surface-adjusting solution BC-3 manufactured by Fuji Photo Film Co., Ltd., and processed at 200 ° C. for 3 minutes using a burning device BP-1300. Next, the printing plate surface was treated with a liquid obtained by diluting Gum GU-7 manufactured by Fuji Photo Film Co., Ltd. with water twice, and allowed to stand for 1 day, and then printed with a Heidel KOR-D machine. Table 1 shows the polymers evaluated and the evaluation results. In addition, JP-A-63-
The compounds shown in No. 226641, which are not included in the scope of the claims of the present patent, are also shown in Table 1 for comparison.
Compounds shown in JP-A-63-226641 and not included in the scope of the claims of the present invention, which are used as comparative compounds, include the following polymer No. C-1 to polymer No. C.
The compound represented by -8 corresponds to this. As is apparent from Table 1, the photosensitive composition of the present invention has extremely excellent performance.

[0087]

[Table 1]

[0088]

[Chemical 32]

Examples 4 to 6 A JIS A 1050 aluminum plate having a thickness of 0.24 mm was supplied by a rotating nylon brush shown below while supplying a suspension of pumice stone and water having an average particle size of about 21 μm to the aluminum surface. Brush grained. The first brush had a bristle length of 100 mm, a bristle diameter of 0.95 mm, and a bristling density of 70 fibers / cm ² , and the second brush had a bristle length of 80 mm, a bristle diameter of 0.295 mm, and a bristling density of 670 fibers / cm ² . The rotation of each brush roll was 250 rpm. After brush graining, rinse well, rinse with 10% sodium hydroxide at 60 ° C for 25 seconds for etching, and rinse with running water.
It was neutralized and washed with 0% nitric acid. These are V _A = 1
Using a sinusoidal alternating current under the condition of 2.7V, 1
Electrolytic surface roughening treatment was carried out in an aqueous solution of nitric acid at a rate of 160 coulomb / dm ^{2 at} the anode time. When the surface roughness was measured, it was 0.79 μm (indicated by _Ra ). Then,
After dipping in a 1% aqueous solution of sodium hydroxide at 40 ° C. for 30 seconds, dipping in a 30% aqueous solution of sulfuric acid and desmutting at 60 ° C. for 40 seconds, and then in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ² . A substrate (II) was prepared by anodizing with direct current so that the weight of the oxide film was 6 g / dm ² .

Then, it was immersed in a 2.5% aqueous solution of sodium silicate at 40 ° C. for 1 minute and dried. The undercoat liquid (A) was applied to the surface of the substrate thus treated under the same conditions as in Examples 1 to 3 and dried. Then, a photosensitive solution (A) (however, the type of polymer was changed to that described in Table 2) was applied on the undercoated substrate in the same manner as in Examples 1 to 3 and dried to obtain a positive photosensitive material. A lithographic printing plate was obtained. Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a metal halide lamp of 2 KW. The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, first, a developing solution (pH 10.5) prepared by diluting the following developing solution-2 with water four times into a developing machine Stablon 900NP manufactured by Fuji Photo Film Co., Ltd. and a finisher FP-2 manufactured by Fuji Photo Film Co., Ltd., respectively. Development was performed under the conditions of charging, a developer temperature of 30 ° C., and a developing time of 12 seconds.

Stock solution for development-2 Sodium carbonate monohydrate 9 g Sodium hydrogencarbonate 1.5 g Diethylenetriaminepentaacetic acid 2 g Sodium metanitrobenzenesulfonate 1 g Water 100 g After development, whether or not an image can be obtained is the same as in Examples 1 to 3. It evaluated by the method. Also, the range of suitable developing conditions (development acceptability), the print-out property after exposure, and the printing durability after burning were evaluated by the same method as in Examples 1 to 3, and the results are shown in Table 1. Shown in 2. As is clear from Table 2, the photosensitive composition of the present invention has extremely excellent performance.

[0092]

[Table 2]

[0093]

[Chemical 33]

Examples 7 to 9 A substrate (II) was prepared by treating an aluminum plate under the same conditions as in Examples 4 to 6. Next, the following photosensitive solution (B) was applied onto this substrate (II) using a whiler, and the temperature was kept at 100 ° C. for 1 hour.
After drying for a minute, a positive photosensitive lithographic printing plate was obtained. The coating amount after drying was about 1.7 g / m ² .

Photosensitive Solution (B) Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 0.45 g Polymer described in Table 1.2 1.2 g Naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.01 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g 4 -[P-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine (hereinafter abbreviated as "triazine A") 0.01 g N- (1,2) -Naphthoquinone-2-diazide-4-sulfonyloxy) -cyclohexane-1,2-dicarbonimide 0.01 Dye which changed counter anion of Victoria Pure Blue BOH [Hodogaya Chemical Co., Ltd.] into 1-naphthalenesulfonic acid 0.045 g Megafac F-177 (Dainippon Ink and Chemicals Co., Ltd. fluorine-based surfactant) 0.015 g methyl ethyl ketone 25 g propylene glycol monomethyl ether 10 g

Next, each of these photosensitive lithographic printing plates was passed through a transparent positive film for 1 m in a vacuum baking frame.
From a distance of 3 kW with a metal halide lamp for 1 minute and then at 30 ° C. for 12 seconds, SiO ₂ / Na ₂ O
Development was carried out with a 3.5% aqueous solution of sodium silicate (pH = 12.4) (molar ratio 2.0). Next, after development, whether or not an image was obtained was evaluated by the same method as in Examples 1 to 3. Also, the range of suitable developing conditions (development acceptability), the print-out property after exposure, and the printing durability after burning were evaluated by the same method as in Examples 1 to 3, and the results are shown in Table 1. Shown in 3. As is clear from Table 3, the photosensitive composition of the present invention has extremely excellent performance.

[0097]

[Table 3]

[0098]

[Chemical 34]

Examples 10 to 12 A substrate (I) was prepared by treating an aluminum plate under the same conditions as in Examples 1 to 3. Next, the photosensitive solution (B) is placed on this substrate.
[However, the type of polymer was changed to that shown in Table 4] was applied and dried in the same manner as in Examples 7 to 9 to obtain a positive photosensitive lithographic printing plate. The coating amount after drying is 2.0
It was g / m ² . Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a metal halide lamp of 2 KW. The exposed photosensitive lithographic printing plate was developed under the following conditions. That is,
First, a developing solution (pH 1) prepared by diluting the following developing stock solution-3 with water in a stablon NP automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
0) and Finisher FP-2 manufactured by Fuji Photo Film Co., Ltd.
Were charged, and development processing was performed under the conditions of a developing solution temperature of 30 ° C. and a developing time of 12 seconds. Stock solution of development-3 benzyl alcohol 10 g triethanolamine 10 g sodium isopropylnaphthalene sulfonate 10 g water 500 g

Then, after the development processing, whether or not an image was obtained was evaluated by the same method as in Examples 1 to 3. Further, in order to examine the range of suitable developing conditions (development acceptability), the above-mentioned developing stock solution-3 was developed with a developing solution diluted 1.5 times with water, and with a developing solution diluted 2 times. The change in tone reproducibility with the case was examined. ○, which has hardly changed
Significant changes are indicated by x, and intermediate evaluations are indicated by Δ. Further, the print-out property after exposure and the printing durability after burning treatment were evaluated in the same manner as in Examples 1 to 3. The results are shown in Table 4. As is clear from Table 4, the photosensitive composition of the present invention has extremely excellent performance.

[0101]

[Table 4]

[0102]

[Chemical 35]

Examples 13 to 14 The following photosensitive solution (C) was applied to a substrate (I) obtained by treating an aluminum plate under the same conditions as in Examples 1 to 3 using a whiler and dried at 100 ° C. for 1 minute. A positive photosensitive lithographic printing plate was obtained. The coating amount after drying was about 1.8 g / m ² .

Photosensitive solution (C) Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallolacetone resin (described in Example 1 of US Pat. No. 3,635,709). 0.45 g Polymer described in Table 5 1.2 g Thermal cross-linking agent D-1 (Compound described in Synthesis Example 1 of Japanese Patent Application No. 4-303515; chemical structural formula is described below in Chemical Formula 36) ( Amount described in Table 5) Naphthoquinonediazide-1,2-diazide-4-sulfonyl chloride 0.01 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g Triazine A 0.01 g N- (1 , 2-Naphthoquinone-2-diazido-4-sulfonyloxy) -cyclohexane-1,2-dicarbonimide 0.01 g Victor Pure Blue BOH [Hodogaya Chemical Co., Ltd.] Dye in which the counter anion is changed to 1-naphthalenesulfonic acid 0.045 g Megafac F-177 (Dainippon Ink and Chemicals Co., Ltd. fluorine-based surfactant) 0 .015 g methyl ethyl ketone 25 g propylene glycol monomethyl ether 10 g

[0105]

[Chemical 36]

Next, each of these photosensitive lithographic printing plates was exposed through a transparent positive film in a vacuum frame from a distance of 1 m with a metal halide lamp of 3 KW for 1 minute, and then the same method as in Examples 1 to 3 was performed. The development process was carried out to obtain a positive image. Next, after performing a burning process under the same conditions as in Examples 1 to 3, printing was performed by using an offset printing machine, and a printing durability test was performed. The results are shown in Table 5. The results of Examples 1 and 2 in which the thermal crosslinking agent D-1 was not added are also shown. As is clear from Table 5,
It can be seen that the photosensitive composition of the present invention can be further improved in burning durability by adding a thermal crosslinking agent.

[0107]

[Table 5]

[0108]

The photosensitive composition according to the present invention has a pH of 12.
It has good developability and development time tolerance with respect to a developer of 5 or less, and is excellent in printout performance and printing durability when heated after development.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshitaka Kawamura 4000 Yoshida-cho, Shizuoka Prefecture Kawajiri, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. Inside the Film Co., Ltd. (72) Inventor Kunimasa Kato 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Sha Shin Film Co., Ltd.

Claims (4)

[Claims] 1. A partial structure represented by the following general formula [I]:
A photosensitive composition containing a polymer compound having
And the exposed portion of the photosensitive composition is an aqueous alkaline solution.
Is dissolved and removed by the above process, and the above-mentioned photosensitive composition which is an unexposed area remains.
The existing part is a photosensitive composition that becomes the ink receiving part.
A photosensitive lithographic printing plate characterized by: [Chemical 1]In the general formula [I], X is an alkylene group or a substituted alkylene.
Group, -CH₂CH₂OCH ₂CH₂-,Represents R₁Is hydrogen atom, halogen atom or alkyl
Represents a group. R₂, R₃Are each independently a hydrogen atom,
Halogen atom, alkyl group, substituted alkyl group, aromatic
Group, substituted aromatic group, -OR_Four, -COOR_Five, -CONH
R₆, -COR₇, Or -CN, or R
₂And R₃May combine with each other to form a ring, and R_Four~ R₇Are each
Represents an alkyl group or aromatic group. n is 2 or 3
Represent. 2. A photosensitive composition containing a polymer compound comprising a repeating unit represented by the following general formula [P]. [Chemical 3] In formula (P), X, R ₁ to R ₇ and n are, X in formula (I), respectively, have the same meanings as R ₁ to R ₇ and n, p is a positive integer. 3. A polymer having a copolymer having a partial structure represented by the general formula [I] and at least one partial structure selected from the following general formulas [II] to [V] as a polymer compound. A photosensitive composition comprising: [Chemical 4] In the general formula [II], R ₈ represents a hydrogen atom, a halogen atom or an alkyl group. A represents a phenylene group or a substituted phenylene group. The B -CO-, or -SO ₂ - represents a. E
It is -CO-R _9, or an -SO ₂ -R _9. R ₉ represents an alkyl group, a substituted alkyl group, an aromatic group or a substituted aromatic group. m and n represent 0 or 1, but m and n are not 0 at the same time. [Chemical 5] In formula [III], R ₁₀ represents a hydrogen atom, a halogen atom,
Or an alkyl group, Y represents an oxygen atom, —NH—, or —N (R ₁₅ ) — (wherein R ₁₅ represents an alkyl group), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ Are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -OR ₁₆ , -OCO-R ₁₇ ,
_{-NHCO-R 18, -NHCONHR 19,} -OCONH
-R ₂₀ , -COOR ₂₁ , -CONHR ₂₂ , -COR ₂₃ ,
Represents a —CONR ₂₄ R ₂₅ , —CN, or —CHO group, or R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are 2
May combine with each other to form a ring, and R _{16 to} R ₂₅ each represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. However, at least one of R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ represents a group other than a hydrogen atom. [Chemical 6] In the general formula [IV], R ₂₆ represents a hydrogen atom, a halogen atom or an alkyl group, and R ₂₇ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group or an aralkyl group. Z represents an oxygen atom or -NH-. [Chemical 7] In the general formula [V], R ₂₈ represents a hydrogen atom, a halogen atom or an alkyl group, and R ₂₉ represents an aromatic group, —CN or —CHO. 4. A partial structure represented by the general formula [I], a partial structure represented by the general formula [II], and at least one partial structure selected from the general formulas [III] to [V]. A photosensitive composition comprising a copolymer having the formula (1) as a polymer compound.