JPH0369956A - Photosensitive lithographic printing plate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a photosensitive lithographic printing plate.

[Background of the invention]

Various photosensitive lithographic printing plates have been proposed in the past.

Some conventional photosensitive lithographic printing plates contain an acrylic resin containing a carboxylic acid group as a binder in their photosensitive layer. However, such a photosensitive lithographic printing plate has a problem in that, when it is used in a negative-working PS plate, for example, its developability is insufficient, particularly when it is stored for a long period of time. In recent years, UV ink (ultraviolet curable ink)
However, photosensitive lithographic printing plates using the above-mentioned photosensitive compositions have a problem of insufficient stiffness resistance when printed with such UV inks.

Furthermore, it is desired that the photosensitive lithographic printing plate has good coating properties of the photosensitive layer. If the coating properties are not good, the reliability will be lowered due to poor coating, and the stiffness resistance may be adversely affected. In addition, as a basic requirement for photosensitive planographic printing plates, it is desired that the sensitivity be further improved.

However, the above developability, storage stability, UV ink suitability,
At present, it is difficult to obtain a coating that satisfies all of the above requirements regarding coatability and sensitivity improvement.

[Purpose of the invention]

The present invention satisfies all of the above requirements and has sufficient developability, especially developability after long-term storage, and also has sufficient stiffness resistance even when printing with UV ink, and has good coating properties. It is an object of the present invention to provide a photosensitive lithographic printing plate which can also achieve improved sensitivity.

[Means and effects for solving the problems] The photosensitive lithographic printing plate of the present invention contains a polymer compound containing a structural unit represented by the following general formula (1) in its molecule, and has a fluorine-containing interface. The above object has been achieved by providing a photosensitive layer containing an activator.

General formula (1) %formula% However, J represents a divalent linking group, and n is O or 1.

The present invention will be further explained below.

First, the photosensitive layer of the photosensitive lithographic printing plate of the present invention contains:
A polymer compound containing a structural unit represented by the general formula CI) in its molecule will be explained.

In the general formula (I), J represents a divalent linking group, and preferably J is a linear or branched alkylene group or arylene group. More preferably, n=1
and J is -CH2- or -CHzc Hz
− This is the case.

The structural unit represented by general formula (I) may be contained in the molecule in the form of a derivative. For example, it may have a substituent. In this way, derivatives of the structure represented by general formula (1) or those containing substituted structural units in the molecule are also included in the present invention.

A polymer compound having a structural unit represented by the general formula CI) in its molecule as described above may be appropriately referred to as a polymer compound according to the present invention.

The polymer compound according to the present invention can function as a binder. This polymer compound can act as an alkali-soluble (or swellable) resin.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention may contain a polymer compound other than the polymer compound according to the present invention.

The polymer compound according to the present invention contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention, and other polymer compounds contained as necessary, preferably have a weight average molecular weight of 20, 000 or more and soo or ooo or less, and is preferably a lipophilic polymer compound. More preferably, the weight average molecular weight is 30,000 or more.
0,000 or less.

Note that the above molecular weight is based on a polystyrene standard determined by GPC.

That is, the weight average molecular weight can be measured by GPC (gel permeation chromatography). Calculation of number average molecular weight MN and weight average molecular weight MW is based on Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan” 8.
By the method described on pages 00 to 805 (1972),
The test shall be performed by leveling the peaks of the oligomer region (by connecting the center lines of the peaks and valleys).

More preferred among the polymer compounds according to the present invention are:
It has a structural unit obtained from a monomer represented by the following general formula (IF) in its molecule.

General formula (II) X-COOH CH,=C OOH However, in general formula (n), X is a divalent linking group.

Preferred specific examples of the compound represented by the general formula [■] include itaconic acid, 1-butene-2,4-dicarboxylic acid,
1-butene-2,3-dicarboxylic acid, 1-pentene-2
, 5-dicarboxylic acid, 1-pentene-2,4-dicarboxylic acid, 1-pentene-2,3-dicarboxylic acid, 1-hexene-2,6-dicarboxylic acid, and the like.

It is essential that the polymer compound according to the present invention contains a structural unit represented by (1)-format (1) in the molecule, and any compound containing such a structural unit can be used. It is particularly preferable to use one containing 2 to 20 mol % of the structural unit represented by the -format (1) in the molecule.

Although the polymer compound according to the present invention can contain structural units other than those represented by the general formula [I] in its molecule, monomers that provide structural units other than those represented by the formula (I) are preferred. Examples include those shown in (1) to (11) below.

(1) Monomers having aromatic hydroxyl groups, such as N-(4
-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o-, m-
, p-hydroxystyrene, o-, m-. p-hydroxyphenyl-acrylate or monomethacrylate.

(2) Monomers having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

(3) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, and N-dimethylaminoethyl acrylate.

(4) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-
(Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate.

(5) Acrylic acid, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,
Acrylamides or methacrylamides such as N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylamide, N-ethyl-N-phenylacrylamide, etc. .

(6) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(7) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(8) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.

(9) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(10) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(11) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc.

(12) Carboxylic acids having unsaturated bonds such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid.

Furthermore, by copolymerizing a monomer that can be copolymerized with the above-mentioned monomer, it may contain a constituent unit other than the structural unit represented by the -S formula (1). Furthermore, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, etc. are also included in those that provide structural units other than those represented by general formula (1). It is not limited to.

In addition, the above copolymer may contain polyvinyl 7L/7 as necessary.
``Tyral resin, polyurethane resin, boria resin,
Epoxy resins, novolac resins, natural resins, etc. may be added.

The following copolymers are particularly preferable as those providing structures other than the structural units of general formula [I].

That is, in the molecular structure, (a) 1 to 50 mol% of a structural unit having an alcoholic hydroxyl group and/or a structural unit having a phenolic hydroxyl group, (b) the following form (I [1] 1 Hz C-.・・・・・・・・・5 to 40 mol% of the structural unit represented by (nu)N (in the formula, R1 represents a hydrogen atom or an alkyl group), IV) Rth-CHz C-・・・・・・・・・ (IV) CO
OR'' (in the formula, R12 represents a hydrogen atom, a methyl group or an ethyl group, and R13 represents an alkyl group or an alkyl-substituted group having 2 to 12 carbon atoms). A polymer compound containing ~60 mol% is preferable, and its weight average molecular weight is 30.000~60 mol%.
Even more preferred are copolymers with a molecular weight of 300,000.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group in (a) above include Japanese Patent Publication No. 52-736
(Meth)acrylic acid varnish R" Hz-c- ...... [■] Coo (CH3CHO), H I5 In the formula, R1 represents a hydrogen atom or a methyl group, RI5 represents a hydrogen atom, a methyl group, an ethyl group or a chloromethyl group,
n represents an integer of 1 to 10.

Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-bitroxypentyl (meth)acrylate, and examples of acrylamides include is N-methylol (meth)acrylamide,
Examples include N-hydroxyethyl (meth)acrylic acid and the like.

Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming the structural unit having a phenolic hydroxyl group in (a) above include N-(4-hydroxyphenyl>-(meth)acrylamide, N-(
2-Hydroxyphenyl)(meth)acrylamide, N
- (meth)acrylamide monomers such as (4-hydroxynaphthyl)-(meth)acrylamide; o-, m
- or p-hydroxyphenyl (meth)acrylate monomer; o-, m- or p-hydroxystyrene monomer, etc. Preferably, Om- or p-
Hydroxyphenyl (meth)acrylate monomer, N
-(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)(meth)acrylamide monomer.

The structural unit having an alcoholic hydroxyl group and/or the structural unit having a phenolic hydroxyl group is selected from the range of 1 to 50 mol%, preferably 5 to 30 mol%, in the polymer compound.

- forming a structural unit represented by the form (I[I);
Examples of monomers having a cyano group in the side chain include acrylonitrile, methacrylonitrile, 2-pentynitrile,
Examples include 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-p-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylatetrile.

The proportion of the structural unit having a cyano group in the side chain contained in the molecule of the polymer compound is preferably selected from the range of 5 to 40 mol%, more preferably 15 to 35 mol%.

- forming a structural unit represented by form (IV);
Monomers having a carboxyester group in the side chain include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, The unit formed from the monomer, including glycidyl acrylate, is preferably selected from the range of 25 to 60 mol%, preferably 35 to 60 mol%, in the polymer compound.

Note that each of the above structural units is not limited to units formed from the monomers listed as specific examples.

As the polymer compound according to the present invention, it is preferable to use, for example, one having the following composition. That is, 3 to 30 mol% of p-hydroxyphenylmethacrylamide (HyPMA) and/or 2, hydroxyethyl methacrylate (HEMA), 5 to 20 mol% of monomers providing the structural unit represented by the - format [■], ethyl 30-70 mol% acrylate, 5-30 mol% acrylonitrile
Those having a composition within the range of can be preferably used.

This composition can act as an alkali-soluble resin.

When carrying out the present invention, a polymer compound other than the polymer compound according to the present invention may be contained in the polymer compound of the photosensitive composition or photosensitive lithographic printing plate. However, in this case, the polymer compound according to the present invention has a molecular weight of 100 to 20
It is preferable that the content is mol%.

Examples of the polymer compound that can be used in combination with the polymer compound according to the present invention include polymers or copolymers of the monomers listed in (1) to (12) above, and the above-mentioned type (
Examples include polymers or copolymers having structural units represented by I[[) to (V).

The polymer compound according to the present invention contained in the photosensitive composition of the present invention and other polymer compounds contained as necessary are preferably combined in a normal amount in the solid content of the photosensitive composition. The content is 40 to 99% by weight, more preferably 50 to 95% by weight.

Next, the photosensitive layer of the photosensitive lithographic printing plate of the present invention contains a fluorine-based surfactant. Examples include (meth)acrylate polymers having an alkyl group; in this case, the number average molecular weight in terms of standard polystyrene is preferably 30,000 or less, more preferably in the range of 2.000 to 10,000. be. Within this range, a sufficient effect of improving coating properties can be obtained.

The acrylate structural unit or methacrylate structural unit of the moiety having a fluorinated alkyl group in the side chain in the (meth)acrylate polymer may have the following format (
Vl) or the following format [■].

General formula (VI) -GHz-C- C=0 0 (CHz)b(CFz)n, CF:+--H.

(In the formula, R is a hydrogen atom or a methyl group, and n is O
~20, a represents an integer of O~2, and b represents an integer of 0~1.

) l-1 General formula [■] CHz C- l-3 υ (In the formula, R is a hydrogen atom or a methyl group, ■-5 VI is O-10° VI is O~2, a is an integer between O and 2 shows.

) The structural unit represented by the general formula (VI) or the following format [■] is specifically exemplified below: l-7 VI-9 1-10 ■-17 ■-11 ■-12 1 -19 ■-13 ■-14 ■-21 ■-15 ■-16 ■-23 υ-shiHz(LJ'z)3shil'l1gυ-L+1lt
Ll-+1'寞J 4Sil'3l-2 l-4 l-6 VI-8 ■-18 ■-20 ■-22 ■-24 ■-25 ■-27 ■-29 ■-38 ■-40 ■ -26 ■-28 ■-30 ■-39 ■-41 ■-31 ■-32 ■-33 ■-34 ■-35 ■-36 ■-37 Hz CH- C=0 0 (Ch)+5CFs ■-2 - cut-CH- ■-6 -CH2 CH Su ■-7 -CH2-CH- υ ■ CH2 CH υ ■-9 CH2-CH- ■ 4 CH.

-CHl-C- υ ■-15 CH3 -CH2-C vinegar ■-16 CH.

-C) 1g -C- ■-10 -CH2-CH- υ ■-11 -CH, -CI- υ ■-12 C.I.

-C1, -C- ■-13 CH.

-CH, -C- ■-17 CH.

-C)l, -C- υ ■-18 CH3 -cnz-c- υ ■-19 CH3 -CI(2-C- ■-20 CH3 ■-23 CH3 -CH, -C- -CI!-C- CI0 0 1 11 O (CHz) zN S (CFz) 16CF3
1 ■-21 CH3 ■-24 CI.

-CH, -C- -CH2-C- C=OO O (CHz) + oN S CF, CF3 υ Also, Having a fluorinated alkyl group in the side chain (meth) Acrylate polymer is Furthermore, the side chain ■ 2 CH3 lekylene oxide group, Or an alkyl group and/or -coz-c- Alternatively, it is preferable that it has an aryl group.

A moiety with an alkylene oxide group in the side chain (meta) As an acrylate structural unit, example Below is the format [■] Is it something that can be expressed as Ru.

General formula [■] ■-5 ■-6 [ 0-(C, IhfiO), H ■-7 ■-8 (In the formula, R represents a hydrogen atom or a methyl group, n is an integer from 1 to 6, m represents an integer of 1 to 10.

) in particular, ■-1 ■ ■-3 ■-4 -CHz-CH- C=O CHZ　-CH CI0 CH3 CH.

0　C4H1lOH 0(CzHaO) zt( 0(C2H3O)! 0 (CJ40) 6H lX-1 1X-2 0-C8゜ 0-C, H5 IX-3 IX-4 etc. can be mentioned.

Furthermore, examples of the (meth)acrylate structural unit having an alkyl group in the side chain include those represented by the following general formula (IX).

-Format (IX) IX-5 IX-6 -cot-c- C=O OC, IHz1%.

IX-7 IX-8 (In the formula, R is a hydrogen atom or a methyl group, n represents an integer of 1 to 22.

) in particular, 0-C? H,S 0　C11H17 1 to -9 IX-10 ■-11 ■-12 OC, Zn2゜ 0 CzoH4+ υ-shiguchi anz* U　　L；zoH4+ etc. can be mentioned.

In addition, the moiety with an aryl group or arylene group in the side chain (
Examples of the meth)acrylate structural unit include those represented by the following format [X].

-3 -4 General formula (X) R.

(In the formula, R8 is a hydrogen atom or a methyl group, and n is O
or 1, and R2 represents a phenyl group or a naphthyl group. ) Specifically, -1 -2 etc. can be mentioned.

The (meth)acrylate polymer having a fluorinated alkyl group in the side chain is composed of structural units represented by the -formats (1) to (V), and the -format (V)
I) - Structural units other than [X], for example, specifically CsF+tSO□N(CJs)CtHn(OCJ6)s
OHCTSF l5cONIIcs■AN” (CHs)
t (Cut)zCOO-CIhCOO- Attract C,F,3SO□NC5HJ”(CHs)zC,F,,
SO□NHCJJ” (CH3) gcz■5Os-O
zCzHsCyF+5CONHCJhN”(CHs)i
It can contain Cr and the like.

In addition to the above-mentioned polymers, examples of the fluorosurfactant preferably used in the present invention include the following fluorosurfactants.

CJ+5COJH4 CsF l? 5OtN(C2Hs) CHzCOOKC
IIF+7SOzNHCJsN”(CHi)zCf-C
? F t 5cONH(CHz) Jゝ(CH3) z
CzH4COO-CsF I? 5OJ(CHs)CHz
CHzOzCCH= CHzCsF l7so□N(C
H,)ICHz CH)7THC00CtHs These fluorine-based surfactants are preferably 0.01% by weight based on the photosensitive composition contained in the photosensitive coating liquid that forms the photosensitive layer of the photosensitive planographic printing plate. The content is preferably 1% by weight, more preferably 0.05% by weight - 0.75% by weight.
% by weight, particularly preferably from 0.08% to 0.5% by weight
It is.

Furthermore, in the present invention, commercially available products can also be used as the fluorosurfactant. Commercially available products include, for example,
Product name: Surflon rS-38J.

rS-382j, rsc-101'', rSC102J,
rSC-103J, rSC-104J (all manufactured by Asahi Kakai ■), Florado rFC-430J, rFC-431
J, rFC-173J (both manufactured by Sumitomo 3M)
, FTOP rEF-352J, rEF-301J, r
EF303J (all manufactured by Shin-Akita Kasei 01), Schwergau Fluor r8035J, r8036J (all manufactured by Schwegmann), rBM-1000J.

Examples include rBM-1100J (both manufactured by BM Himy).

Even in the case of using the above-mentioned commercial products, the preferable content of the fluorine-containing surfactant in the photosensitive layer is the same as described above.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention can contain various photosensitive compounds.

For example, a diazo resin can be preferably included.

Any diazo resin can be used in the present invention.

In the present invention, as the diazo resin, a co-condensed diazo resin containing an aromatic compound having one or more of at least one of a carboxyl group or a hydroxyl group and an aromatic diazonium compound as a constituent unit can be preferably used.

Such an aromatic compound having a carboxyl group and/or a hydroxyl group is one that contains an aromatic ring substituted with at least one carboxyl group and/or an aromatic ring substituted with at least one hydroxyl group in the molecule. In this case, the carboxyl group and the hydroxyl group may be substituted on the same aromatic ring, or may be substituted on different aromatic rings. This carboxyl group or hydroxyl group may be bonded directly to the aromatic ring or may be bonded via a bonding group.

Preferred examples of the aromatic group include aryl groups such as phenyl and naphthyl groups.

In the co-condensed diazo resin that can be used in the present invention, the number of carboxyl groups bonded to one aromatic ring is preferably 1 or 2, and the number of hydroxyl groups bonded to one aromatic ring is 1 to 3. is preferred. When a carboxyl group or a hydroxyl group is bonded to an aromatic ring via a bonding group, examples of the bonding group include an alkylene group having 1 to 4 carbon atoms.

Specific examples of the aromatic compound containing a carboxyl group and/or hydroxyl group as a constitutional unit of the co-condensed diazo resin include benzoic acid, 〇-chlorobenzoic acid, m-
Chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4-(m-
methoxyanilino)benzoic acid, 4-(p-methylbenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, phenol, (o
, m, 'p)-cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycine, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone , p-hydroxybenzyl alcohol, 4-chlororesorcinol, biphenyl-4,4゛-diol, 1,2゜4-benzenetriol, bisphenol A12゜4-dihydroxybenzophenone, 2,3.4-trihydroxybenzophenone,
p-hydroxyacetophenone, 4.4-dihydroxydiphenyl ether, 4,4''-dihydroxydiphenylamine, 4.4''-dihydroxydiphenyl sulfide, cumylphenol, (o, m, p) -chlorophenol, (o, m, p )-bromophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid,
6-laurylsalicylic acid, 6-stearylsalicylic acid, 4
．． 6-dimethylsalicylic acid, p-hydroxybenzoic acid,
2-methyl-4-hydroxybenzoic acid, 6-methyl-4
-Hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2゜4
-dihydroxy-6-methylbenzoic acid, 2,6-dihydroxybenzoic acid, 2,6-dihydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid Acid, gallic acid, phloroglucincarboxylic acid, 2.4.5-)dihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p-tolyl) gallic acid, protocate Quoyl-gallic acid, 4,6-cyhydroxyphthalic acid, (2,4-
';Hydroxyphenyl) vinegar! , (2゜6-hydroxyphenyl>acetic acid, (3,4,5-trihydroxyphenyl>acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4-(p-hydroxyphenyl)methylbenzoic acid) !, 4-(O-hydroxybenzoyl)
Benzoic acid, 4-(2,4-dihydroxybenzoyl)
Benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid 9
．． 4-(p-hydroxyanilino)benzoic acid, bis(3
-carboxy-4-hydroxyphenyl)amine, 4-
Cp-hydroxyphenylsulfonyl)benzoic M, 4
-(p-hydroxyphenylthio)benzoic acid and the like can be mentioned. Among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid,
Metachlorobenzoic acid.

As the aromatic diazonium compound used as the structural unit of the co-condensed diazo resin, diazonium salts such as those listed in Japanese Patent Publication No. 49-48001 can be used, but diphenylamine-4-diazonium salts are particularly preferred. Diphenylamine-4-diazonium salts are
Although derived from 4-agonodiphenylamines, such 4-amino-diphenylamines include 4-amino-diphenylamines.
-Amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino- 3-methyldiphenylamine,
4-amino-3-nitoxydiphenylamine, 4-amino-3-β-hydroxy-ethoxydiphenylamine, 4-aminodiphenylamine-2-sulfonic acid, 4-
Examples include amino-diphenylamine-2-carboxylic acid and 4-amino-diphenylamine-2'-carboxylic acid. Particularly preferred are 3-methoxy4-aminodiphenylamine and 4-amino-diphenylamine.

As the co-condensed diazo resin that can be used in the present invention, those represented by the following format [X] are preferred.

- Format [X] In the general formula (X), A is a group derived from an aromatic compound having at least either a carboxyl group or a hydroxyl group, and examples of such aromatic compounds include those listed above. be able to.

In the formula, Ro, R2 and R1 represent a hydrogen atom, an alkyl group or a phenyl group, R1° represents a hydrogen atom, an alkyl group or a phenyl group, and X represents a counter anion. n preferably represents a number from 1 to 200.

When a co-condensed diazo resin is used in the present invention, it is more preferable to use it in combination with a condensed diazo resin obtained by condensing an aromatic diazonium compound.

In this case, the co-condensed diazo resin is preferably used in an amount of 5% by weight or more in the diazo resin, and the condensed diazo resin is preferably used in an amount of 95% by weight or less in the diazo resin.

Further, in this case, the weight % ratio of co-condensed diazo resin to condensed diazo resin is particularly preferably 30-70:70-30 in terms of achieving both excellent sensitivity and developability.

The above-mentioned co-condensed diazo resins and condensed diazo resins used in combination with these or independently as diazo resins are:
Known methods such as Photographic Science and Engineering (Photo, Sci,
Eng, Volume 17, Page 33 (1973), U.S. Patent No. 2,063,631, U.S. Patent No. 2,679,498. It is obtained by polycondensation of salts, aromatic compounds having carboxyl and hydroxyl groups, and aldehydes, such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone and acetophenone.

Furthermore, these aromatic compounds, aromatic diazo compounds, and aldehydes or ketones having carboxyl and/or hydroxyl groups in their molecules can be freely combined with each other, and two or more of each may be mixed and co-condensed. is also possible.

The molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazonium compound is preferably 1:0.1 to 0.1:1,
More preferably 1:0.5 to 0.2=1, still more preferably 1:1 to 0.2:1.

In this case, the molar ratio of the sum of aromatic compounds and aromatic diazonium compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually preferably 1:0.6 to 1.2, more preferably 1:0.6 to 1.2. A co-condensed diazo resin can be obtained by mixing the components at a ratio of 1:0.7 to 1.5 and reacting at a low temperature for a short period of time, for example, about 3 hours.

The counter anion of the diazo resin includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. Those that form such anions include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids, and typical examples include methanesulfonic acid, chloroethanesulfonic acid, etc. , dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4
- Aliphatic and aromatic sulfonic acids such as acetylbenzenesulfonic acid and dimethyl-5-sulfoisophthalate, 2
．． 2", 4. 4'-tetrahydroxybenzophenone, 1.2.3-trihydroxybenzophenone, 2
．． Hydroxyl group-containing aromatic compounds such as 2°,4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, CIO,,10
Examples include perhalogen acids such as , and the like.

However, it is not limited to this. Among these, particularly preferred are hexafluorophosphoric acid, 2-hydroxy-
4-methoxybenzophenone-5-sulfonic acid.

The above-mentioned co-condensed diazo resin can have an arbitrary molecular weight by varying the molar ratio of each monomer and the condensation conditions. In the present invention, in general, those having a molecular weight of about 400 to io, o o oO can be effectively used, more preferably about 800 to 5.
000 is appropriate.

In addition, in the present invention, other than the above-mentioned co-condensed diazo resins, those that can be preferably used as diazo resins include, for example, the above-mentioned Photographic Science &
Engineering (Photo.

Sci, Eng.) Vol. 17, p. 33 (1973), and U.S. Pat.
No. 98, 3゜050.502 specifications, JP-A-59
A diazo resin obtained by condensing a diazo compound and an active carbonyl compound, such as formaldehyde, acetaldehyde or benzaldehyde, etc., in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid, the manufacturing method of which is described in Publication No. 78340, etc. Examples include diazo compounds and diphenyl resins whose production methods are described in Japanese Patent Publication No. 49-4001.

Among the above, the diazo resin that can be preferably used in the present invention is represented by the following formula (XI), and contains 20 mol% or more of a resin in which n in each formula is 5 or more, more preferably, It contains 20 to 60 mol%. In the formula, R1'''R3, R1゜, X, n are the above-mentioned -form (Xf
) has the same meaning as that in ). -Format [X! ], examples of the alkyl group and alkoxy group of R1, R2 and R3 include alkyl groups having 1 to 5 carbon atoms and 1 to 5 carbon atoms.
-5 alkoxy groups, and examples of the alkyl group for R include alkyl groups having 1 to 5 carbon atoms.

- Format (XI) Such a photosensitive diazo resin can be produced according to a known method, for example, the method described in the above-mentioned Photographic Science and Engineering and other U.S. patent specifications cited above. .

At that time, when polycondensing the diazonium salt and the aldehyde, the molar ratio of both is usually 1:o, 6-1:
2. A highly sensitive diazo resin can be obtained by charging preferably at a ratio of 1:0.7 to 1:1°5 and reacting at a low temperature for a short period of time, for example, 3 hours or less below 10°C.

As the counter anion of the diazo resin represented by the general formula (XI), the same counter anions as those mentioned for the co-condensed diazo resin can be mentioned.

In the practice of the present invention, the photosensitive layer of the photosensitive lithographic printing plate is
Contains 3 to 50% by weight, more preferably 3 to 30% by weight of diazo resin as a photosensitive substance.
,,7:4. ; Margin below: H; r: 1 "°Pani" In carrying out the present invention, the photosensitive layer of the photosensitive lithographic printing plate is
It can contain any organic acid, inorganic acid, or acid anhydride.

Although the organic acid is arbitrary, monocarboxylic acids and polycarboxylic acids having at least one carboxyl group are preferred. Malic acid, tartaric acid, and polyacrylic acid (such as those commercially available under the trade name Jurimer) can be preferably used.

As the inorganic acid, phosphoric acid or the like can be used. Acid anhydrides are also optional, such as acetic anhydride, propionic anhydride, benzoic anhydride, those derived from aliphatic/aromatic monocarboxylic acids, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride. Examples include those derived from aliphatic/aromatic dicarboxylic acids.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention can contain a dye, particularly a dye that changes color from colored to colorless or changes color upon processing. Preferably, a pigment that changes from colored to colorless is contained.

In carrying out the present invention, the following can be mentioned as dyes that can be preferably used.

That is, for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.)
, Crystal Violet, Brilliant Green, Ethyl Violet, Seven To, Methyl Violet, Methyl Green, Erythrosin B, Pesic Tsuksin, Malachite Green, Oil Red, M-Cresol Purple,
Triphenylmethane type, diphenylmethane type, oxazine type, xanthine type, iminonaphthoquinone type, azomethine type or anthraquinone represented by rhodamine B, auramine, 4-p-dimethylaminophenyliminonaphthoquine, cyano-p-diethylaminophenyl acetanilide, etc. Examples of pigments that change color from colored to colorless or to a different color can be cited.

Particularly preferably, triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, and Victoria Viewer Blue BOH is particularly preferred).

The above-mentioned color changing agent is usually added in the photosensitive composition from about 0.5 to about 10
It is preferable to contain the amount by weight, more preferably about 1% by weight.
Contain up to 5% by weight.

In the photosensitive lithographic printing plate of the present invention, the photosensitive layer includes:
Furthermore, various additives can be added.

That is, as additives, for example, alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants [e.g., Pluronic L-64 (manufactured by Asahi Denka Co., Ltd.) to improve coating properties, etc. )], plasticizers for imparting flexibility and abrasion resistance to the coating film (e.g., butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), fat-sensitizing agents for improving the fat-sensitivity of image areas (for example, JP-A-55-527) Half esters of the styrene-maleic anhydride copolymers described above with alcohol, etc.), stabilizers [e.g., phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4- Methoxy
2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.)]. The amount of these additives is
Although it varies depending on the object and purpose of use, it is generally preferably 0.01 to 30% by weight based on the total solid content.

Next, the photosensitive lithographic printing plate of the present invention can be obtained by coating it on a support to form a photosensitive layer, but in order to provide the photosensitive layer on the support, a photosensitive composition must be prepared. A predetermined amount of a polymer compound, other additives, etc. is mixed with an appropriate solvent (methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol,
A method can be used in which a coating solution of the photosensitive composition is prepared by dissolving the photosensitive composition in dimethylformamide, dimethyl sulfoxide, water, a mixture thereof, etc., and the solution is coated on a support and dried. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 50% by weight.

Application methods for coating liquid include dip coating, roll coating, reverse roll coating, air doctor coating, blade coating, front coating, knife coating, squeeze coating, gravure coating, cast coating,
Methods such as curtain coating, extrusion coating, etc. can be used. The coating film thickness is 0.1 to 5 g/
rd is preferred. Moreover, the preferable drying temperature is 20 to 150
℃, more preferably in the range of 30 to 100℃.

In the photosensitive lithographic printing plate of the present invention, various supports can be used to form the photosensitive layer. Particularly preferred is an aluminum plate. However, if an aluminum plate is used without treatment, there are problems in that the adhesion of the photosensitive composition is poor and the photosensitive composition decomposes. In order to eliminate this problem, various proposals have been made in the past.

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (US Pat. No. 2,714°066), a method in which the surface is treated with an organic acid salt (US Pat. No. 2,714,
No. 066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2
, 946,683), a method of anodizing, and a method of treating with an aqueous solution of an alkali metal silicate after anodizing (US Pat. No. 3,181,461).

In a preferred embodiment of the present invention, the surface of the aluminum plate (including the alumina laminate; the same applies hereinafter) is degreased and then grained by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, etc. It is preferably grained by an electrolytic ethosing method which produces a deep, uniform grain.

The anodizing treatment is carried out, for example, in an aqueous solution of an inorganic salt such as phosphoric acid, chromic acid, boric acid, or sulfuric acid, or an organic acid such as oxalic acid, or a mixture of two or more of these acids, preferably in an aqueous sulfuric acid solution. This is done by passing an electric current through an aluminum plate as an anode. The amount of anodic oxide film is 5-6
0■/d m” is preferable, more preferably 5~
30■/dm''.

When carrying out the pore sealing treatment in carrying out the present invention, it is preferable to add a sodium silicate aqueous solution with a concentration of 0.1 to 3% at a temperature of 8.
This treatment is carried out by immersion at 0 to 95°C for 10 seconds to 2 minutes.

More preferably, it is then soaked in water at a temperature of 40 to 95°C for 10 seconds to 2
Soak and process for a minute.

The photosensitive lithographic printing plate of the present invention can be exposed and developed by conventional methods. That is, for example, a negative leaf image can be obtained with respect to the original image by exposing the transparent original image having a line image, halftone image, etc. to light, and then developing with an aqueous developer.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

Any developer can be used to develop the photosensitive lithographic printing plate of the present invention as long as it can develop the plate.

Preferably, a developer containing a specific organic solvent, an alkaline agent, and water as necessary components can be used.

The specific organic solvent herein refers to one that can dissolve or swell the non-exposed area (non-image area) of the layer made of the photosensitive composition of the present invention when contained in the developer.
Furthermore, the solubility in water at room temperature (20°C) is 10.
% or less of organic solvent is preferred. Such organic solvents only need to have the above characteristics, and are not limited to the following:
Examples of these include carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone. , ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methyl amyl alcohol, n-amyl alcohol, methyl amyl alcohol: such as xylene alkyl-substituted aromatic hydrocarbons; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developer is preferably about 1
-20% by weight, and particularly preferable results are obtained when the content is 2-20% by weight.

On the other hand, preferred alkaline agents contained in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium di- or tri-phosphate, and sodium carbonate; , inorganic alkali agents such as ammonium, (B) mono-, di- or trimethylamine, mono.

Examples include organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediamine, and the like.

The content of these alkaline agents in the developer is usually 0.
It is preferably 0.05 to 4% by weight, more preferably 0.5 to 2% by weight.

Further, in order to further improve storage stability, rigidity resistance, etc., it is preferable to include a water-active sulfite in the developer. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the developer composition is usually preferably 0.05 to 4% by weight, more preferably 0.1 to 1% by weight.

Bringing such a developer into contact with the photosensitive layer after development and exposure,
If rubbed with a developer, after 10 to 60 seconds at room temperature to 40°C, there will be no adverse effect on the exposed areas of the photosensitive layer. explain. As a matter of course, the present invention is not limited to the following examples.

Prior to specific description of Examples, the polymer compound and diazo resin used in each Example will be explained.

Him (1) Under a stream of human nitrogen, 2-hydroxyphenyl methacrylate (H
yPMA) 17.0g, ethyl acrylate (EA
) 57.0g 1 Acrylonitrile (AN) 12
．． 7 g of itaconic acid (IA), and 1.64 g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60° C. for 6 hours with stirring. After the reaction is complete,
The reaction solution was poured into water to precipitate the polymer compound. This was collected by filtration and vacuum-dried at 50°C overnight.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
and gel permeation chromatography (
As measured by GPC (polystyrene standard), the weight average molecular weight was 80.000.

2-Hydroxyethylmethacryle) (H
EMA) 13.3g, ethyl acrylate (HA)
50.0g, acrylonitrile (AN) 15.9g
, itaconic acid (IA) (11.7 g), and azobisisobutyronitrile (1.64 g) were dissolved, and the mixture was centrifuged at 60° C. for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was collected by filtration and vacuum-dried at 50°C overnight.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
The weight average molecular weight was 75.000 as measured by gel permeation chromatography (GPC: polystyrene standard).

(3) In a mixed solvent of 65 g of acetone and 65 g of methanol under a nitrogen stream, p-hydroxyphenyl methacrylate) (
HyPMA) 17.7g, ethyl acrylate (EA)
57.0g, acrylonitrile (AN) 12.7g,
After the reaction, 7.7 g of methacrylic acid (MAA) and 1.64 g of azobisisobutyronitrile were dissolved and the mixture was refluxed at 60°C for 6 hours while stirring, and the reaction solution was poured into water to dissolve the polymer. The compound was precipitated. Filter this out,
It was vacuum-dried at 50° C. for one day and night.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
and gel permeation chromatography (
As measured by GPC (polystyrene standard), the weight average molecular weight was 78,000.

Diazo 8(1) p-diazodiphenylamine sulfate 14.5 g (
50 mmol) was dissolved in 40 g of concentrated sulfuric acid under water cooling.

To this reaction solution, 1.05 g (35 mmol) of rose formaldehyde was slowly added dropwise. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. after that,
Stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol, it was dissolved in 100-pure water, and an aqueous solution in which 6.8 g of zinc chloride was dissolved was added to this solution. The resulting precipitate was filtered off, washed with ethanol, and dissolved in 150-pure water. An aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved was added to this solution, and the resulting precipitate was filtered off, washed with water and ethanol, and dried at 25°C for 3 days to obtain the diazo resin (1). Obtained.

Diazo UIMU Mu p-hydroxybenzoic acid 3.5 g (25 mmol)
, and p-diazodiphenylamine sulfate 21.75
g (75 mmol) was dissolved in 90 g of concentrated sulfuric acid under water cooling. To this solution was slowly added 2.7 g (90 mmol) of rose formaldehyde. At this time, the addition was made so that the reaction temperature did not exceed 10°C. After stirring the reaction solution for 2 hours, it was added dropwise to 11 ethanol, and the resulting precipitate was filtered out and washed with ethanol. Precipitate at 200 r
An aqueous solution in which 10.5 g of zinc chloride was dissolved in pure water was added. The resulting precipitate was filtered, washed with ethanol, and then dissolved in 300-pure water. In this solution,
An aqueous solution containing 13.7 g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and then dried at 25°C for - days to obtain a diazo resin (2).

In the synthesis of diazo resin (2), 4.2 g (25 mmol) of p-methoxybenzoic acid was used instead of p-hydroxybenzoic acid, and diazo resin (3) was synthesized in the same manner. ) was obtained.

Next, Examples and Comparative Examples will be described.

Examples 1 to 4, Comparative Example 1.2 A grained and anodized aluminum plate was used as a support, and a photosensitive solution having the following composition was coated on the support using a roll coater to a solid content of 1. The coating was applied to a coating amount of 8 g/rrf, and then dried to obtain a photosensitive planographic printing plate.

The combinations of the polymer compound, diazo resin, and fluorosurfactant shown in the composition are shown in Table-1.

Table 1 FC-430: Fluorine surfactant manufactured by 3M Company ○: Excellent, ○△: Good, Δ: Slightly poor, ×: Poor The hall was evaluated.

Here, the term "marangoni" refers to hazy, spiral-shaped coating unevenness that occurs on the coated surface after coating and drying.

This kind of uneven coating is thought to be caused by the Marangoni effect, which is caused by local differences in the surface tension of the wet photosensitive layer due to the temperature drop accompanying the volatilization of the solvent.

A pinhole refers to a circular white spot in the photosensitive layer that appears on the coated surface. Further, vertical streaks are a state in which the thickness of the photosensitive layer is non-uniform, which appears in the running direction of the support because the coating solution is not smoothed.

In addition, a negative transparent original image was placed on the obtained sample, and after exposure for 30 seconds from a distance of 60CIII with a 2KW metal halide lamp, the sample was placed in a conical S plate developer 5DN-21 at 27℃.
After immersion for 20 seconds, development was performed by rubbing lightly with absorbent cotton.

At this time, the sensitivity was compared depending on the number of solid steps of the step wedge.

The resulting plate was printed on a Heidelberg GTO printing machine,
Developability was evaluated based on the amount of dirt on the paper surface.

In addition, the sample after coating was forcibly stored (temperature: 55°C, humidity: 20°C).
%RH for 5 days), exposure, development, and printing were performed in the same manner as described above, and the storage developability was evaluated.

In addition, printing was performed using UV ink (Kasai Best Cure BF Beni, manufactured by Kasai Shiki), and the number of printable sheets of each sample was compared.

In addition, after exposure and development, the solid area of the plate was rubbed with a sponge containing UV ink cleaning oil (Solfit, manufactured by Kuraray) for 1 minute, and the density of the solid area of the plate was measured with a densitometer (red light). Compare the density difference before and after rubbing with UV ink cleaning oil, and
V-in hand wash oil resistance was evaluated.

The results are shown in Table-3.

Margin below Table-3 (a) Immediately after coating, printed with a plate that was made.

02 No stains on the paper surface at all.

△: Partially stained.

×: Overall staining.

(b) After coating, forced storage, plate making, and printing.

The levels of ○, Δ, and × are the same as in (a).

fc) The number of sheets printed at the time when poor inkling was observed due to thinning or chipping of the photosensitive layer in the image area due to wear.

(d) Decrease in solid density when the solid area of the plate after R light and development is rubbed with UV cleaning oil. (Densitometer, red light) From Tables 2 and 3, it can be seen that Examples 1 to 4 had good coating properties, excellent developability and storage developability, and high sensitivity.

Furthermore, it has good UV ink stiffness resistance, good UV wash oil resistance, and is found to be excellent in UV ink suitability.

On the other hand, Comparative Example 1 has excellent developability, storage developability, and UV ink suitability, but has poor coating properties and somewhat low sensitivity.

In addition, Comparative Example 2 has slightly poor developability when not stored, and is considerably poor when developed after storage. It also has difficulty in coating and has somewhat low sensitivity. Furthermore, the UV ink printing durability and UV washing oil resistance are also significantly inferior.

It has excellent UV ink printing durability and UV washing oil resistance, which is significantly inferior, and has a strong printing durability when UV ink is used, and has the effect of being less likely to cause dye loss due to UV ink washing oil.

Further, the photosensitive printed matter of the present invention has the effects of high sensitivity and good coating condition.

Claims (1)

[Claims] 1. A photosensitive layer containing a polymer compound containing a structural unit represented by the following general formula [I] in its molecule and a fluorine-based surfactant is provided. Characteristic photosensitive planographic printing plate. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ However, J represents a divalent linking group, and n is 0 or 1.