JP3130166B2 - Photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate provided with a photosensitive layer containing a photocrosslinkable polymer which is crosslinked by a cycloaddition reaction.

[0002]

2. Description of the Related Art Photocrosslinkable materials which are crosslinked by a cycloaddition reaction are well known, and they are widely used as main components of photosensitive compositions used for producing photosensitive lithographic printing plates and the like. As such a photocrosslinkable polymer,
A polymer having a maleimide group in a side chain, a cinnamyl group having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group or a chalcone group in a side chain or a main chain. These polymers are useful and some have been put to practical use. In particular, polymers having a maleimide group in the side chain and polyester resins having a cinnamic acid skeleton in the molecular chain produced by condensation of phenylenediacrylic acid or its alkyl ester with glycol have relatively high sensitivity. .

On the other hand, since the photosensitive layer containing the photo-crosslinkable polymer does not have a property of discoloring upon exposure (printing out property), it has been desired to provide a visually distinguishable performance. Many bakeout compositions are known [for example, "Light-Sensiti" by J. KOSAR.
ve Systems, J. Wily and Sons "(New York 1965) pp3
85-401], and combinations of various compounds are known in the fields of photosensitive lithographic printing plates, photoresists and the like (for example, Japanese Patent Publication No. 40-2203, Japanese Patent Application Laid-Open No.
No. 8128, JP-A-54-74728 and U.S. Pat. No. 4,139,390). Among such bakeout compositions, combinations of organic polyhalogen compounds or photooxidants with various leuco dyes are known as being particularly effective (for example, Photogr. Sci. Eng., 5 , 98).
-103, 1961 and U.S. Patent No. 3,042,515).

[0004] However, when the print-out property is imparted by a leuco dye, a large amount of leuco dye is added or separately added to facilitate plate inspection for distinguishing an image area from a non-image area after development. It is necessary to add a coloring agent. As described above, it is not preferable to include a large amount of an additive such as a photooxidant, a leuco dye, and a coloring agent in the photosensitive layer because the inherent properties of the photosensitive layer, for example, sensitivity and printing durability are reduced. . By the way, as a photosensitive composition satisfying both printing performance such as sensitivity and printing durability and good print-out property, a combination of a photoacid generator described in JP-A-4-303838 and a dye capable of fading or discoloring by acid is disclosed. Is used as a baking agent. However, with the recent increase in work efficiency, further improvement in printing durability after exposure and development is expected.

[0005]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive layer containing a photocrosslinkable polymer, which has excellent printability while maintaining the excellent sensitivity of the photosensitive layer, and has the above-mentioned disadvantages. An object of the present invention is to provide a photosensitive lithographic printing plate that gives an excellent printing plate with improved printing durability.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have improved the photoacid generator used for imparting print-out properties to improve the object. Have been achieved, leading to the present invention. That is, the present invention relates to a photosensitive lithographic printing plate provided with a photosensitive layer containing a photocrosslinkable polymer having a photodimerizable unsaturated bond, wherein a strong acid is generated in the photosensitive layer by exposure to the following general formula [I A photosensitive lithographic printing plate characterized by containing a compound which is discolored or discolored by an acid or an acid.

[0007]

Embedded image Formula (I) wherein R ¹ is a hydrogen atom, a halogen atom, —NO ₂ , —CN,
It represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or -X ¹ -R ¹⁰ . Where X ¹ is -O-,
-S -, - CO-O - , - O-CO -, - NR 11 -CO-
Or shows a -CO-NR ^11, R ¹⁰ represents a substituent alkyl group which may have a, optionally substituted aryl group or optionally substituted aralkyl group.
R ¹¹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ^{2 to} R ⁸ may be the same or different from each other, and include a hydrogen atom, a halogen atom,
O ₂ , —CN, an alkyl group which may have a substituent,
It represents an aryl group which may have a substituent, an aralkyl group which may have a substituent, or -X ² -R ¹² . Here, X ² represents -O-, -S-, -CO-O-, -O-CO-,-
NR ¹³ -CO- or -CO-NR ¹³ - indicates, R ¹² is an optionally substituted alkyl group, which may have an optionally substituted aryl group or a substituted group R ¹³ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent. Y
Represents -O- or -S-. R ⁹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
Provided that when R ^{1 to} R ⁸ are hydrogen atoms and Y is —O—, R ⁹
Has 2 or more carbon atoms. Hereinafter, the present invention will be described in detail. The photocrosslinkable polymer having an unsaturated bond capable of photodimerization used in the present invention has a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylideneacetyl group, a chalcone group, or the like in a side chain or a main chain. Polymers.

As a polymer having a maleimide group in the side chain, Japanese Patent Application Laid-Open No. 52-988 (corresponding to US Pat. No. 4,079,041)
Gazette, German Patent No. 2,626,769, European Patent No. 21,019, European Patent No. 3,552, and Die Angewandte Makromolekulare Chemie 1
15 (1983), pp. 163-181, a polymer having a maleimide group represented by the following general formula (II) in the side chain, and JP-A Nos. 49-128991 and 49-18991.
No. 128992, No. 49-128993, No. 50-5379, No. 50
No.-5377, No.50-5379, No.50-5378, No.50-
No. 5380, No. 53-5298, No. 53-5299, No. 53-53
No. 00, No. 50-50107, No. 51-47940, No. 52-
13907, 50-45076, 52-121700, 5
Nos. 0-10884 and 50-45087, German Patent 2,349,9
And polymers having a maleimide group in the side chain represented by the following general formula (III) described in JP-A Nos. 48 and 2,616,276.

[0009]

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Wherein R ¹⁴ and R ¹⁵ each independently represent an alkyl group having up to 4 carbon atoms, or R ¹⁴ and R ¹⁵ together form a 5- or 6-membered carbon R ¹⁶ represents an aromatic group, and R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group or a cyano group.) These polymers have an average molecular weight of 1,000 or more, preferably 20,000 to 300,000. It is. Further, these polymers have an average of two or more maleimide groups per molecule in the side chain.

In order to make these polymers having a maleimide group in the side chain soluble or swellable in alkaline water, they can be achieved by including an acid group in the polymer.
Specific examples of the acid group include a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, an alkali metal salt or an ammonium salt thereof, and a pKa that is dissociated with alkaline water.
In the acid group _include, -SO 2 NHCO _-, - CON
HCO -, - SO ₂ NHCOO-, and a 4-hydroxyphenyl group. These monomers having an acid group and a monomer having a maleimide group are, for example, 10 /
90-50 / 50, preferably 20 / 80-40 / 6
The polymer of the present invention can be easily obtained by copolymerizing at a ratio of 0 (molar ratio). The acid value of the maleimide polymer having an acid group is preferably in the range of 30 to 300, and more preferably 50 to 250. Preferred examples of the copolymerizable monomer having an acid group include vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid, maleic anhydride, and itaconic anhydride.

[0012] Among these polymers having an acid value,
Dee Angebandute Macromolecule Kemi
ー (Die Angewandte Makromolekulare Chemie)128
(1984), pages 71-91.
N- [2-methacryloyloxy) ethyl] -2,3
-Dimethyl maleimide and methacrylic acid or acrylic
Copolymers with acids are useful. Further synthesis of this copolymer
When copolymerizing the third component vinyl monomer
Therefore, to easily synthesize multi-component copolymers according to the purpose
Can be. For example, as a vinyl monomer of the third component,
Alkyl whose homopolymer has a glass transition point below room temperature
Using methacrylates and alkyl acrylates
Therefore, flexibility can be given to the copolymer. Shinna
Mill group, cinnamoyl group, cinnamylidene group, cinnami
Has a redeneacetyl group, chalcone group, etc. in the side chain or main chain
Among the other photocrosslinkable polymers of the present invention,
Those having a cinnamoylene group include, for example, US
No. 3030208, U.S. Patent Application Nos. 709496 and 828455
There are photosensitive polyesters described. Poly above
The ester is a suitable polycarboxylic acid or a suitable
Suitable with lower alkyl esters of boronic acid or chloride
Polyhydric alcohols in the presence of an esterification catalyst
It is made by turning.

The following are examples of the solubilized alkaline water of these polymers. That is, an unsaturated double bond capable of photodimerization adjacent to an aromatic nucleus in a main chain as described in JP-A-60-191244,
Polyester prepolymers having a carboxyl group at the side chain and a hydroxyl group at the terminal have a chain extender having two or more functional groups capable of reacting with hydroxyl groups in the molecule, such as diisocyanate compounds, diphenyl terephthalate, diphenyl carbonate and terephthaloyl bis (N -Caprolactam) or a polyester prepolymer or a polyurethane prepolymer having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus in the main chain and a hydroxyl group at a terminal in the main chain. Examples of the extender include a photosensitive polymer obtained by reacting pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride to introduce a carboxyl group into a side chain. Furthermore, an acid value of 20 having a functional group capable of photodimerization on the side chain and a carboxyl group on the side chain.
To 200 alkaline water soluble or swellable photosensitive polymers. These photosensitive polymers are described in JP-A-62-175729, JP-A-62-175730, JP-A-63-25443, JP-A-63-218944 and JP-A-63-218944.
It is described in each gazette of 218945. The photocrosslinkable polymer used in the present invention has a molecular weight of 1,000 or more,
It is desirable to use those having a molecular weight of preferably 10,000 to 500,000, particularly preferably 20,000 to 300,000. The amount of the photocrosslinkable polymer to be added to the entire photosensitive layer composition is 10 to 99% by weight, preferably 50 to 99% by weight.

In the present invention, it is desirable to use a sensitizer in the photosensitive layer. As such a sensitizer,
A photosensitizing polymer capable of sensitizing the above photocrosslinkable polymer,
It is preferable to use a triplet sensitizer having a maximum absorption in the range of 0 nm or more. Specific examples include benzophenone derivatives, benzuanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, naphthofuranone compounds, pyrylium salts, thiapyrylium salts, and the like. Can be mentioned. Specifically, Michler Kane, N,
N'-diethylaminobenzophenone, benzuanthrone, (3-methyl-1,3-diaza-1,9-benzo)
Anthrone picramide, 5-nitroacenaphthene, 2-
Chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone
1-ethylcarboxylate, 2-nitrofluorene,
2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,3-carbonyl-bis (7-diethylaminocoumarin), 2,4,6-triphenylthiapyrylium perchlorate, 2- (P-chlorobenzoyl) naphthothio Other than azole, JP-B-45-8832, JP-A-52-1297
No. 91, JP-A-62-294238, JP-A-2-173646, JP-A-2-131236, EP 368327, JP-A-2-2365
Sensitizers described in JP-A-52-54, JP-A-3-54566 and JP-A-4-259915. The addition amount of these sensitizers is about 1 to 20% by weight, more preferably 3 to 10% by weight of the photosensitive layer.

In the present invention, the dyes which fade or discolor depending on the acid used include diphenylmethane, triphenylmethane, thiazine, oxazine, xanthine, anthraquinone, iminonaphthoquinone, and the like.
Azomethine-based and azo-based dyes are effectively used.
Examples of these are as follows. Brilliant Green, Eosin, Ethyl Violet, Erythrosin B, Methyl Green, Crystal Violet, Basic Fuchsin, Phenolphthalene, 1,3-Diphenyltriazine, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinaldin Red, Rose Bengal, Methanil yellow, thymol sulfophthalein, xylenol blue, methyl orange,
Orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurine 4B, α-naphthyl red, Nile blue 2B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin,
Oil Blue # 603 [Orient Chemical Industry Co., Ltd.
Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Co., Ltd.) Industrial Co., Ltd.), Oil Red RR (Orient Chemical Co., Ltd.), Oil Green # 502 (Orient Chemical Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Industry Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, fast acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2- Carboxanilino-4-
p-diethylaminophenyliminonaphthoquinone, 2-
Carbostearylamino-4-p-dihydrooxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3
-Methyl-4-p-diethylaminophenylimino-5
-Pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, methyl yellow, p-diethylaminoazobenzene, 2,4-dinitro-5-chloro-2'-acetoamino-4'-diethylamino-5 '-Methoxyazobenzene.

These may be used in combination of two or more.
Next, the compound represented by the general formula [I] that generates a strong acid upon exposure will be described. In the general formula, examples of the halogen atom as R ^{1 to} R ⁸ include F, Cl, Br and I atoms. The alkyl group as R ^{1 to} R ¹³ may be any of linear, branched and cyclic as long as it has 1 to 18 carbon atoms. Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, an isoamyl group, a 2-ethylhexyl group, and a cyclohexyl group. The substituted alkyl group as R ^{1 to} R ¹³ may be a C ^{1 to} C 12 alkyl group such as a halogen atom such as a Cl atom, a C ^{1 to} C 8 alkoxy group such as a methoxy group, a phenoxy group, a benzylthio group, And the like, and a group having 1 to 18 carbon atoms in the whole substituted alkyl group is preferable.
Specifically, a 4-chlorobutyl group, a 4-ethoxybutyl group, a 2-butoxyethyl group, a 4-phenoxybutyl group,
And a 2-benzylthioethyl group. The aryl group as R ^{1 to} R ¹³ is preferably a monocyclic or bicyclic aryl group, and includes, for example, a phenyl group, an α-naphthyl group, a β-naphthyl group and the like. The aryl group as R ^{1 to} R ¹³ may be the above-mentioned aryl group, for example, an alkyl group having 1 to 12 carbon atoms such as a methyl group or an ethyl group, for example, a methoxy group,
An alkoxy group having 1 to 8 carbon atoms such as an ethoxy group, for example, those substituted with a halogen atom such as a Cl atom are included. Specific examples include a methylphenyl group, a t-butylphenyl group, a t-octylphenyl group, a chlorophenyl group, a methoxyphenyl group, and a methoxynaphthyl group.

The aralkyl group as R ^{1 to} R ¹³ is preferably an alkyl group having 1 to 18 carbon atoms substituted with a monocyclic or bicyclic aryl group. Examples include a phenylethyl group, a 1-methylbenzyl group, an α-naphthylethyl group, a β-naphthylethyl group, and a phenylbutyl group. The substituted aralkyl group represented by R ^{1 to} R ¹³ may be a substituted alkyl group as described above substituted with an aryl group, an alkyl group as described above substituted with a substituted aryl group, or a substituted alkyl group as described above. And a group in which a substituted aryl group is substituted. Specifically, a 2-chloro-2-phenylethyl group,
p-chlorobenzyl group, p-methoxybenzyl group, p-
Examples include a nitrobenzyl group, a p-methoxybenzyl group, a 2-chloro-2- (p-chlorophenyl) ethyl group. Among the compounds represented by the above general formula [I], particularly preferred are compounds wherein R ^{1 to} R ⁸ are hydrogen atoms and Y is-
A compound which is O-, and wherein R ⁹ is an alkyl group which may have a substituent having 4 to 10 carbon atoms or an aralkyl group which may have a substituent having 7 to 9 carbon atoms, and R
^{1 to} R ⁵ , R ⁷ and R ⁸ are hydrogen atoms, R ⁶ is an alkoxy group, Y is —O—, and R ⁹ is an alkyl group which may have a substituent, It is a compound having 4 to 10 carbon atoms in total of R ⁶ and R ⁹ . The above general formula [I]
Compounds are from Organic Synthesis Vol. II, PP. 494-496
The compound can be synthesized from the corresponding amino compound by a diazotization reaction and a salt exchange reaction according to the method described in (1943).
Further, the corresponding amino form (A) can be easily synthesized by a reduction reaction of a nitroso form (B), a reduction reaction of a nitro form (C), a hydrolysis reaction of an amide form (D), or the like. That is, the synthesis scheme is as follows.

[0018]

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[0019]

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[0020]

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More specifically, the reaction route i) is described in Compound Synthesis Example 1, and the reaction route ii) is described in Synthesis Example 2.
Reaction route iii) is described in Synthesis Example 3. Examples of the compound represented by the above general formula [I] which generates a strong acid upon exposure used in the photosensitive layer of the present invention include, but are not limited to, the following.

[0022]

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[0023]

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[0024]

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[0025]

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In addition, it is preferable to use a compound such as an organic halogen compound or orthoquinonediazidosulfonyl chloride in combination. The ratio of the dye as described above to the compound capable of generating a strong acid upon exposure represented by the general formula [I] is such that the compound capable of generating a strong acid is about 0.01 part by weight to about 100 parts by weight, relative to 1 part by weight of the dye. Preferably, it is in the range of 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. The photosensitive layer of the present invention can contain a binder if necessary, and is usually selected appropriately from linear organic polymers. Specific examples of the binder include chlorinated polyethylene, chlorinated polypropylene, polyacrylate alkyl ester, acrylate alkyl ester, acrylonitrile, vinyl chloride, styrene, a copolymer with at least one kind of monomer such as butadiene, polyamide, Examples include methylcellulose, polyvinyl formal, polyvinyl butyral, methacrylic acid copolymer, acrylic acid copolymer, and itaconic acid copolymer. Further, if necessary, another dye pigment or the like can be contained in addition to the dye which is discolored by the acid.

Further, the photosensitive layer of the present invention may contain a plasticizer. As such a plasticizer, a dialkyl phthalate such as dibutyl phthalate or dihexyl phthalate, an oligoethylene glycol alkyl ester, or a phosphate plasticizer may be used.
In addition, it is also preferable to use a negative working diazo resin in the photosensitive layer. These diazo resins function as an adhesive for a support having a hydrophilic surface or as a crosslinking agent.

Examples of such a diazo resin include 4-diazo-diphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N -Ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-
Methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene,
1-diazo-4-N, N-dimethylaminobenzene, 1
-Diazo-4-morpholinobenzene, 1-diazo-
2,5-dimethoxy-4-p-trimercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-
Diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo- 2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-trimercaptobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N-diethylaminobenzene, 1-diazo-3-methyl-4-
Pyrrolidinobenzene, 1-diazo-2-chloro-4-
N, N-dimethylamino-5-methoxybenzene, 1-
Diazo-3-methoxy-4-pyrrolidinobenzene, 3-
Diazo monomers such as methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3-isopropoxy-4-diazodiphenylamine, formaldehyde, acetaldehyde, propion Aldehyde, butylacetaldehyde, isobutyraldehyde, benzaldehyde or a condensing agent such as glyoxylic acid, aldehyde having a carboxyl group such as malonaldehyde acid, etc. in a molar ratio of 1:10 to 1: 0.05, respectively.
Preferably, a reaction product of an anion and a condensate obtained by condensing in a usual manner in an acidic medium at a ratio of 1: 2/1: 0.2 is used. Examples of such anions include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitroortho-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4 , 6-Trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2 −
Mention may be made of anions such as methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid and paratoluenesulfonic acid. Among them, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-
Anions of alkyl aromatic sulfonic acids, such as dimethylbenzene sulfonic acid, are preferred.

Further, a diazo resin having a carboxyl group or a hydroxy group is preferable for solubilization in an alkaline developer. Such a diazo resin can be obtained by co-condensing an aromatic compound having at least one carboxyl group with the above diazo monomer compound. Specific examples of the aromatic compound having a carboxyl group or a hydroxy group include salicylic acid, alkyl group-substituted salicylic acid, benzoic acid, hydroxybenzoic acid, gallic acid, hydroxyphthalic acid, phenylacetic acid, hydroxyphenylacetic acid, phenoxyacetic acid, and Compounds obtained by substituting these compounds with alkyl, alkoxy, carboxy, and the like. In addition, the diazo compounds described in JP-B-49-48001 are also suitable. Co-condensed diazo resins containing, as constituent units, an aromatic compound having at least one carboxyl group or a hydroxy group and an aromatic diazonium compound can be prepared by a known method, for example, Photographic Science and Engineering (Photo. Sci. ., Eng.) Volume 17, Page 33 (197
3) According to the methods described in U.S. Pat. Nos. 2,063,631 and 2,679,498, an aromatic diazonium compound, an aromatic compound having a carboxyl group, and aldehydes in sulfuric acid, phosphoric acid, or hydrochloric acid. It can be obtained by polycondensing paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

The aromatic compound having a carboxyl group or a hydroxy group in the molecule, the aromatic diazonium compound and the aldehydes or ketones can be freely combined with each other. Is also possible. Furthermore, cocondensable phenols having no carboxyl group hydroxy group can be added for cocondensation. At that time, the charged molar ratio of the aromatic compound having a carboxyl group and the aromatic diazonium compound is 1: 0.1 to 0.1: 1, preferably 1: 0.2 to 0.2.
The ratio is from 2 to 1, more preferably from 1: 0.5 to 0.2: 1. In this case, the total of the aromatic compound having a carboxyl group or a hydroxy group and the aromatic diazonium compound and the aldehydes or ketones are usually 1: 0.
The co-condensed diazo resin can be obtained by charging the mixture at 6 to 1.2, preferably 1: 0.7 to 1.5, and reacting at a low temperature for a short time, for example, about 3 hours. In addition, diazo resins described in JP-A-3-2868 and diazo resins having sulfonic acid or phosphoric acid in the molecule described in JP-A-3-240060 and JP-A-4-25845 are also preferable. . The amount of the diazo resin added to the entire photosensitive layer composition is preferably 0.1 to 15% by weight, more preferably 0.3 to 5% by weight.

The above-mentioned photosensitive layer is prepared by adding a photosensitive composition comprising the above components to, for example, 2-methoxyethanol, 2-methoxyethyl acetate, methyl cellosolve, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl. Acetate, acetone,
Methyl ethyl ketone, ethylene dichloride, methyl lactate, ethyl lactate, methanol, dimethylformamide,
It is formed by dissolving in a suitable solvent such as ethanol or methyl cellosolve acetate alone or in a mixed solvent in which these are appropriately combined, and coating the solution on a support. The coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying are suitable, preferably from 0.5 to 5 g / m ^2.

The surface of the photosensitive layer of the present invention may be subjected to a matting process in order to further enhance the adhesion to the film.
These are described in JP-A-55-12974 and JP-A-58-12974.
Compounds and methods described in -182636 can be used. The support having a hydrophilic surface used in the present invention is preferably a dimensionally stable plate. Such dimensionally stable plate-like materials include those conventionally used as supports for printed matter, and they can be suitably used in the present invention. Examples of such a support include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.),
Metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, Examples include plastic films such as polycarbonate and polyvinyl acetal, and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited. Among these supports, the aluminum plate is preferable because it is extremely stable in dimension, 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 bonded 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 preferable that a surface treatment such as a graining treatment and an anodic oxidation treatment is performed. Further, in order to enhance the hydrophilicity of the surface, it is preferable to perform a dipping treatment 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 grained and then immersed in an aqueous solution of sodium silicate, and an anodized aluminum plate as described in JP-B-47-5125. After immersion, an immersion treatment in an aqueous solution of an alkali metal silicate is also preferably used. Also, U.S. Pat.
Electrodeposition of silicate as described in US Pat. No. 8,662 is also effective. Further, a surface obtained by combining the electrolytic grain disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503 with the above-described anodic oxidation treatment and sodium silicate treatment. Processing is also useful.
Further, as disclosed in JP-A-56-28893, a brush grain, an electrolytic grain, an anodizing treatment and a sodium silicate treatment which are sequentially performed are also suitable. Further, after these treatments are performed, a water-soluble resin such as polyvinylphosphonic acid, a polymer or a copolymer having a sulfonic acid group in a side chain, or a primer coated with polyacrylic acid is also preferable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, This is performed to improve the adhesion. As a developer for the photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, Inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium hydrogen carbonate, sodium carbonate, aqueous ammonia, and aqueous solutions of organic amine compounds such as monoethanolamine and triethanolamine are suitable. It is added in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

If necessary, an organic solvent such as sodium organic sulfonate and other surfactants and alcohols may be added to the alkaline aqueous solution. Preferred examples of the organic solvent include benzyl alcohol, 2-phenoxyethanol, 2-butoxyethanol, and n-propyl alcohol. In addition, it is also preferable to add a diazo solubilizer, for example, a reducing substance such as a sulfite, methylresorcin, or a pyrazolone compound. U.S. Pat.Nos. 3,475,171 and 3,6
No. 15,480 can be mentioned.
Further, the developing solutions described in JP-A-50-26601, JP-B-56-39464 and JP-B-56-42860 are also excellent as developing solutions for the photosensitive lithographic printing plate of the present invention.

As a method of developing a photosensitive lithographic printing plate image-exposed using the above-described developing solution, a developing solution is charged into a developing tank, and the photosensitive lithographic printing plate is immersed in the developing solution. A method of repeatedly using a developing solution such as a method of passing a developing solution or a method of spraying a developing solution in a developing tank, or methods described in JP-A-61-243455 and JP-A-62-2254.
As disclosed in Japanese Patent Application Laid-Open No. H10-260, an amount of a developing solution necessary for developing one photosensitive lithographic printing plate is applied to the plate surface, and the developing solution is developed only with the applied developing solution, and then the developing solution is discarded. Although various systems such as a disposable developing system that does not reuse the developing solution can be used, in the present invention, a system in which the developing solution is used repeatedly is preferable. preferable. The composition of the developer and replenisher of the developing method for performing such replenishment and the replenishment method are described in JP-A-54-62004, JP-A-55-22759 and JP-A-55-22759.
Nos. 5-115039, 56-12645, 58-95349,
JP-A-64-21451, JP-A-1-180548, JP-A-2-30
No. 65, which can be suitably used in the developing method of the present invention.

The image exposure is performed by using a photosensitive lithographic printing plate with a light source rich in ultraviolet rays such as a metal halide lamp and a high-pressure mercury lamp, and then treated with the above-mentioned developer to remove unexposed portions of the photosensitive layer. If necessary, a desensitizing treatment after washing, a desensitizing treatment as it is, or a treatment with an aqueous solution containing an acid, followed by a desensitizing treatment to obtain a printing plate. If necessary, after development, post-exposure or burning treatment may be performed to increase the degree of crosslinking in the image area.

The photosensitive lithographic printing plate of the present invention has excellent printing properties, developability, printing durability and printing durability.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples. "%" Indicates% by weight unless otherwise specified.

Synthesis Example 1 (Synthesis of Compound Example 1) m-Hydroxydiph
Phenylamine (185 g), nC₈H₁₇Br (193g), K_Two
CO _Three(140 g), N, N-dimethylacetamide (D
MAc) (300 g) in a flask at 160 ° C. for 5 hours
After heating and stirring for a while, the mixture is crystallized with ice water (5 L). Profit
Crystal (m-octyloxydiphenylamine)
With EtOH (1000 g), concentrated H_TwoSO_Four(200g)
And NaNO_Two(75 g) of a 10% aqueous solution is added dropwise. Dripping
After one day, the pH was adjusted to 10 or more with 30% NaOH water.
And then Na_TwoS_TwoO _Four(300 g) and stirred for 3 hours
Thereafter, it is crystallized with ice water (5 l). The resulting crystal
(4-amino-3-octyloxydiphenylamine)
Was dissolved in MeOH (1000 g), concentrated HCl (100 g),
Under ice cooling, NaNO_Two(75 g) of a 10% aqueous solution are added dropwise. drop
After stirring for 3 hours, KPF₆10% of (184g)
When an aqueous solution is added, a yellow precipitate precipitates. Filter this precipitate
After drying and drying, the target compound, Compound 1 was obtained.
Was. (Total yield: 58%, 272 g) Physical properties: m.p. 64.0
° C, d.p. 120.0 ° C, UV absorption in MeOH λ_max366.0n
m

[0039]

Synthesis Example 2 (Synthesis of Compound Example 2) Hydroquinone (1
10 g), nC ₄ H ₉ Br (280 g), K ₂ CO ₃ (150 g)
g) and DMAc (200 g) in a flask at 120 ° C. for 5 minutes.
After heating and stirring for an hour, crystallize with ice water (5 liters).
The obtained crystals (1,4-dibutoxybenzene) are converted to CHCl
₃ (500 g) and SO ₂ Cl ₂ (150 g) is added dropwise. After the dropwise addition, the mixture was stirred for 2 hours, and after removing the solvent and the like under reduced pressure, acetic acid (1000 g) was added, followed by concentrated HNO ₃ (110 g).
g) is added dropwise under ice cooling. After the dropwise addition, the mixture was stirred for 3 hours,
Liters). The obtained crystal (2,5-dibutoxy-4-chloronitrobenzene) was dissolved in N, N-dimethylformamide (DMF) (500 g), and aniline (100 g) and NaH (25 g) were added little by little.
After addition, heat at 180 ° C. for 12 hours. After stirring, water (3 l) and methanol (3 l) are added, and the mixture is left for 3 hours under ice cooling to crystallize. The obtained crystals (2,5-dibutoxy-4-nitrodiphenylamine) were dissolved in isopropyl alcohol (1000 g), NH ₄ Cl (53 g),
Water (50 g) and Fe (300 g) were added, and the mixture was stirred at 90 ° C. for 3 hours, filtered through celite, concentrated HCl (100 g) was added to the filtrate, and a 10% aqueous solution of NaNO ₂ (70 g) was added dropwise under ice cooling. I do. After the addition, the mixture was stirred for 1 hour, and further KPF ₆ (190 g)
When a 10% aqueous solution of is added, a yellow precipitate precipitates. The precipitate was collected by filtration and dried to obtain the desired compound of Compound Example 2. (Total yield 36%, 175 g) Physical properties dp
135.0 ° C, UV absorption in MeOH λ _max 402.0 nm

[0040]

Synthesis Example 3 (Synthesis of Compound Example 3) 2-amino-5-nitrophenol (154 g), K ₂ CO ₃ (150 g), DM
Ac (200 g) was placed in a flask and stirred at 150 ° C. for nC
₆ H ₁₃ Br (170 g) is added dropwise. Five hours after the addition, the mixture is crystallized with ice water (5 liters). The obtained crystals were dissolved in isopropyl alcohol (1000 g) and NH ₄ Cl (5
3 g), water (50 g) and Fe (300 g) were added, and the mixture was stirred at 90 ° C. for 5 hours, filtered through celite, and concentrated. The obtained solid was dissolved in acetonitrile (500 g), and acetyl chloride (80 g) and triethylamine (110 g) were dissolved.
After adding g) and stirring for 4 hours, the filtrate is concentrated. The obtained solid is dissolved in DMF (500 g), NaH (25 g) is added little by little, and the mixture is stirred. 2,5-dichloronitrobenzene (192 g) is added, and the mixture is stirred at 150 ° C. for 10 hours. After stirring, the mixture was crystallized with water (5 liters), and CH ₃ OH (1000 g) and concentrated HCl (100 g) were added to the obtained crude crystals.
After stirring at 60 ° C. for 1 hour, cooling to ice temperature precipitates crystals. The resulting crystals (4-amino-3-hexyloxy-
2'-nitro-4'-chlorodiphenylamine hydrochloride)
Was dissolved in DMF (500 g), concentrated HCl (15 g) was added, and a 10% aqueous solution of NaNO ₂ (70 g) was added dropwise.
After stirring for 2 hours, a 10% aqueous solution of KPF ₆ (190 g) is added, and a yellow precipitate precipitates. The precipitate was collected by filtration and dried to obtain the target compound (Compound Example 3). (Total yield 2
1%, 109 g) Physical properties dp 130.0 ° C, UV absorption in MeOH λ _max 360.
0 nm In addition, Compound Examples 4 to 17 are also described in Synthesis Examples 1 to 3 described above.
Can be synthesized by the same method as described above.

[0041]

EXAMPLE An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then washed thoroughly with water. 10%
After etching by dipping in sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This was converted to 160 coulombs / cm 2 in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of V _A = 12.7 V.
Electrolytic surface-roughening treatment was performed with an anode charge of dm ² . When the surface roughness was measured, it was 0.6 μ (Ra display).
Subsequently, it was immersed in a 30% aqueous solution of H ₂ SO ₄ ,
After desmutting at 2 ° C. for 2 minutes, the amount of the anodic oxide film was 2.5 in a 20% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ² .
g / m ² for 2 minutes. Then 7
It was immersed in a 2.5% aqueous solution of sodium silicate at 0 ° C. for 1 minute, washed with water, and dried.

Next, the following photosensitive compositions 1 to 22 were applied to a weight after drying of 1.0 g / m ^2, and then dried at 80 ° C. for 2 minutes to obtain a negative photosensitive lithographic plate. Printing plates [A] to [Q] and photosensitive lithographic printing plates [S] for comparison
[W] was obtained. Photosensitive composition 1-22 ○ Methyl methacrylate / N- [6- (methacryloyloxy) hexyl] -2,3-dimethylmalemit / methacrylic acid = 10/60/30 (molar ratio) Copolymer [Mw = 3. 0 × 10 ⁴ (GPC)] 5 g ○ 0.30 g of a sensitizer represented by the following structural formula

[0043]

Embedded image

○ Dodecylbenzenesulfonate of formaldehyde human cocondensate of 4-siasophenylphenylamine and phenoxyacetic acid 0.20 g ○ Photoacid generator (Table 1) 0.15 g ○ Victoria Pure Blue BOH (Hodogaya Chemical) 0.14 g ○ Phosphorous acid 0.03 g ○ Propylene glycol monomethyl ether 50 g ○ Methyl ethyl ketone 50 g ○ Methyl alcohol 30 g ○ Megafac F-177 (Dainippon Ink Chemical Co., Ltd., fluorine-based nonionic surfactant) 0.10 g obtained The obtained photosensitive lithographic printing plate was contact-exposed through a negative film. Exposure was performed by irradiating a 2 kw ultra-high pressure mercury lamp for 60 seconds. Then, potassium silicate 1.5
Development was carried out at 25 ° C. for 30 seconds in a weight% aqueous solution. After washing with water
The gum solution was applied and printed with a KORD printing machine manufactured by Heidelberg. Table 1 shows the results.

[0045]

[Table 1] Table 1 感光 Photosensitive lithography Photosensitive light strong acid baking ⁽¹⁾ Developability Printing performance Printing durability Printing plate composition Generator (△ D) (10,000 sheets) ───────────────────────── ─────────── [A] 1 Compound Example 1 0.12 Good No stain 6.0 [B] 2 Compound Example 0.14 Good No stain 6.0 [C] 3 Compound Example 0.12 Good No stain 6.0 [D] 4 Compound Example 4 0.12 Good No stain 6.5 [E] 5 Compound Example 5 0.12 Good No stain 5.5 [F] 6 Compound Example 6 0.13 Good No stain 5.5 [G] 7 Compound Example 7 0.14 Good Stain None 5.5 [H] 8 Compound Example 8 0.12 Good No stain 5.5 [I] 9 Compound Example 9 0.12 Good No stain 6.0 [J] 10 Compound Example 10 0.12 Good No stain 6.0 [K] 11 Compound Example 11 0.1 1 Good No stain 6.0 [L] 12 Compound Example 12 0.1 2 Good No stain 6.5 [M] 13 Compound Example 13 0.1 1 Good No stain 6.5 [N] 14 Compound Example 14 0.1 3 Good No stain 6.0 [ O] 15 Compound example 15 0.1 4 Good No stain 6.0 [P] 16 Compound example 16 0.1 1 Good No stain 6.0 [Q] 17 Compound example 17 0.1 3 Good No stain 6.5 Comparative [S] 18 Compound C1 0.12 Good Stain None 4.5 Comparative [T] 19 Compound C2 0.03 Good No stain 5.0 Comparative [U] 20 Compound C3 0.12 Poor Dirty 6.0 There are residuals Comparative [V] 21 Compound C4 0.13 Poor Dirty 6.0 There are residuals Comparative [W] 22 Compound C5 0.00 Good No stain 5.5 mm 1) Density difference between exposed and unexposed areas due to Macbeth density system

[0046]

Embedded image The photosensitive lithographic printing plates [A] to [Q] according to the present invention have good printing properties, developability, printing performance and printing durability, whereas the comparative printing plate [S] has printing durability. Low
The printing plate [T] has poor printing properties and low printing durability,
The printing plates [U] and [V] have poor developability and printing performance, and the printing plate [W] has poor printing properties.

Continuation of front page (56) References JP-A-4-303838 (JP, A) JP-A-4-274429 (JP, A) JP-A-3-288853 (JP, A) JP-A-3-129352 (JP) JP-A-4-153655 (JP, A) JP-A-2-18947 (JP, A) JP-A-3-2868 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB G03F 7/004 G03F 7/00 503 G03F 7/038

Claims (1)

(57) [Claims] 1. A photosensitive lithographic printing plate provided with a photosensitive layer containing a photocrosslinkable polymer having a photodimerizable unsaturated bond, wherein a strong acid is generated in the photosensitive layer by exposure to light. A photosensitive lithographic printing plate characterized by containing a compound represented by the formula (1) and a dye which is discolored or discolored by an acid. Embedded image In the formula, R ¹ is a hydrogen atom, a halogen atom, —NO ₂ , —C
N represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or -X ¹ -R ¹⁰ . Here, X ¹ is -O-, -S-, -CO-O-, -O-CO-, -NR
¹¹ -CO- or -CO-NR 11 ^- indicates, R ¹⁰ may have an optionally substituted alkyl group, an optionally substituted aryl group or a substituted group Represents an aralkyl group. R ¹¹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ^{2 to} R ⁸ may be the same or different from each other, and include a hydrogen atom, a halogen atom, —NO ² , —CN, an alkyl group which may have a substituent, and an aryl group which may have a substituent. , An aralkyl group which may have a substituent or —X ² —R ¹² . Where X ² is -O-, -S
—, —CO—O, —O—CO—, —NR ¹³ —CO— or —CO—NR ¹³ —, wherein R ¹² has an alkyl group which may have a substituent, and a substituent. R ¹³ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aryl group which may have a substituent. An aralkyl group which may have a substituent is shown. Y is -O-
Or -S-. R ⁹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. Where R
^{When 1 to} R ⁸ are hydrogen atoms and Y is —O—, R ⁹ has 2 or more carbon atoms.