JPH02115846A - Damping-waterless planographic printing plate - Google Patents

Abstract

PURPOSE:To increase the adhesive strength of the photosensitive layer and fluoroplastic layer of the plate material and to enhance the plate wear of the printing plate by incorporating an ethylenic unsatd. addition polymerized compd. into the photosensitive layer. CONSTITUTION:The ethylenic unsatd. addition polymerized compd. (A), a photopolymn. initiator and diazo resin are incorporated into the photosensitive layer of the plate material constituted by providing the photosensitive layer and the fluoroplastic layer successively via a primer layer at need on a base consisting of an Al plate, etc. A polymer having the unsatd. group expressed by the formula in the side chain is usable for the component A. In the formula, R<1> to R<3> denote H, halogen, etc.; X denotes -C(R<4>R<5>)-, carboxyl; R<4>, R<5> are synonymous with R<1>; Z denotes O, S, etc. A copolymer of methacrylic acid and benzyl methacrylate, etc., are usable for the component A.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a lithographic printing plate material that does not require dampening water, and more specifically, is capable of maintaining good sensitivity and has a structure in which a fluororesin layer and a photosensitive layer are combined. The present invention relates to an excellent lithographic printing plate material that does not require dampening water and has improved adhesion between the plates and stiffness resistance when used for printing.

[Background of the Invention] Conventionally, as a planographic printing plate material that does not require dampening water, for example, JP-A-58-215411 discloses a copolymer containing a specific fluorine-containing acrylic monomer and a monomer having a photosensitive group. A plate material is disclosed in which a photosensitive layer is provided and the photosensitive layer has ink repellency.

However, this plate material cannot be said to have sufficient adhesion, and therefore, printing plates obtained from this plate material do not have sufficient rigidity and have the disadvantages of poor shadow area and small dot reproducibility. there were.

However, when the content of photosensitive groups is increased in an attempt to improve the rigidity resistance and reproducibility of the printing plate, there is a problem in that the ink repellency decreases and background smearing tends to occur.

In addition, the above-mentioned lithographic printing plate material can be developed with a fluorine-based developer such as meta-xylene hexafluoride, but cannot be developed with a developer other than fluorine-based. Furthermore, due to the strong reactivity of fluorine, it is not easy to handle, and there are problems in waste liquid treatment.

In addition, lithographic printing plate material that does not require dampening water (hereinafter referred to as r
"Print materials". ) is known, in which a photosensitive layer and an ink repellent layer are sequentially coated on a support. By exposing and developing this plate material, a lithographic printing plate (hereinafter referred to as "printing plate" as necessary) that does not require dampening water can be obtained.

As an example of using a fluororesin as such an ink repellent layer, for example, WO33-02175 specifies:
In a plate material having a photosensitive layer and an ink repellent layer in this order on a support, a fluororesin layer made of a perfluoroalkyl compound having a metal atom and a functional group bonded to the metal atom is used as the ink repellent layer. The plate material is disclosed. This printing plate material has the characteristic that high resolution can be obtained because the presence of metal atoms improves adhesion and the thickness of the ink repellent layer can be made extremely thin, around 10 mm. There is a problem that the printing durability is insufficient and streak-like stains occur on the entire plate surface.

In addition, methods for improving the adhesion between the photosensitive layer and the fluororesin layer include, for example, a method of providing an intermediate layer and a method of improving the photosensitive layer. In particular, when improving the photosensitive layer, Depending on the type of photosensitive layer, it has a great effect on the adhesion with the fluororesin layer, and it is also necessary to consider the effect on the photosensitive characteristics of the photosensitive layer. For example, when a diazo resin is used as a photosensitive layer, the fluororesin layer provided on the photosensitive layer does not have sufficient adhesion between them, and when a photopolymerizable composition is used as a photosensitive layer, fluorine resin Not only does it have insufficient adhesion to the resin layer, but it also has the disadvantage of being easily affected by oxygen and having unstable sensitivity.

Therefore, the present inventors conducted various studies on the adhesion between the photosensitive layer and the fluororesin layer, focusing on improving the photosensitive layer. By using a saturated addition polymer compound, it is possible to obtain a plate material that provides stable sensitivity, has excellent storage stability, has good adhesion to the fluororesin layer, and has excellent printing properties such as printing durability. This finding led to the present invention.

[Objective of the Invention] The object of the present invention is to provide printing that has stable sensitivity and excellent storage stability, has better adhesion to the fluororesin layer, and has excellent printing properties such as printing durability when printed. An object of the present invention is to provide a lithographic printing plate material that does not require dampening water and can be used to form a plate.

[Structure of the Invention] Therefore, the object of the present invention is to provide a lithographic printing plate material that does not require dampening water and has a photosensitive layer and a fluororesin layer in this order on a support, in particular, the photosensitive layer is (A) ethylenically unsaturated. This was achieved using a lithographic printing plate material that does not require dampening water and is characterized by containing an addition polymerization compound, (B) a photopolymerization initiator, and (c) a diazo resin.

[Function] The present invention uses a specific ethylenically unsaturated addition polymer compound as one component of the photosensitive layer, thereby contributing to the adhesion between the photosensitive layer and the fluororesin layer in cooperation with the diazo resin. ,
Increases the adhesive strength between these layers and provides strong adhesion. As a result, a printing plate with excellent printing properties such as stiffness resistance can be obtained.

[Specific configuration of the present invention] The present invention will be explained in more detail below.

The lithographic printing plate material of the present invention that does not require dampening water has a
The basic layer structure is a photosensitive layer and a fluororesin layer in this order, but the present invention is characterized by the combination of a photosensitive layer and a fluororesin layer. It contains a saturated addition polymerization compound, (B) a photopolymerization initiator, and (c) a diazo resin.

(A) Ethylenically unsaturated addition polymer compound The ethylenically unsaturated addition polymer compound used in the present invention (hereinafter referred to as A polymer) contains an unsaturated group in the side chain of the backbone polymer,
It is characterized in that this unsaturated group consists of a group represented by the general formula [11].

General formula [I] [In the formula, R1, R2 and R3 may each be the same or different, and represent hydrogen, halogen, carboxyl, sulfo, nitro, cyano, amide, amino and each substituent. is a group selected from alkyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, alkylsulfonyl and arylsulfonyl which may have

Moreover, x is a group consisting of -C(R'RS)- (R4 or Rs has the same meaning as R1n 2 and R3 above.)
, or carboxyl group, Z is oxygen, sulfur, NH
Alternatively, it is a group selected from NR (R represents an alkyl group). ] The substituents R1 to R3 represented by the above general formula [I] used in the present invention will be explained in more detail below.

The alkyl groups of RI to R3 may be linear, branched, or cyclic, and those having 1 to 7 carbon atoms are preferable, and these alkyl groups further include an alkoxy group having 1 to 2 carbon atoms, and an alkyl group having 1 to 2 carbon atoms. It may have 1 to 3 substituents such as an alkoxycarbonyl group, phenyl group, or hydroxy group.

The aryl group of R1, vt3 is preferably a phenyl group or a furyl group, and these include a halogeno group (e.g. chloro, pro-thousand, etc.), a hydroxy group, an alkyl group having 1 to 7 carbon atoms, an aryl group (e.g. phenyl, methoxyphenyl, etc.), an alkoxy group having 1 to 7 carbon atoms, a nitro group, an amino group, an N,N-dialkylamino group, and the like.

The alkoxy group for R1-R3 is preferably one having 1 to 7 carbon atoms, and the aryloxy group is preferably a phenyloxy group, which has a substituent such as an alkyl group or alkoxy group having 1 to 7 carbon atoms. You may do so.

The alkylamino group of R1-R3 has 1 to 1 carbon atoms.
5 is preferred, and the arylamino is preferably a phenylanino group or a naphthylamino group.

The alkylsulfonyl group of R1 to R' has 1 to 1 carbon atoms.
15 is preferred, and the arylsulfonyl is preferably phenylsulfonyl, which has 1 to 1 carbon atoms.
It may have a substituent such as an alkyl group having 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an amino group.

In the A polymer used in the present invention, what is used as the backbone polymer is not particularly limited. Examples include copolymers made of halides, and copolymers of maleic acid, itaconic acid, etc. are also used. In this copolymer, the comonomers to be copolymerized include styrene or its alkyl-substituted conductor, acrylic acid alkyl ester, -
Examples include aryl acrylate, alkyl methacrylate, aryl methacrylate, and fatty acid vinyl ester.

Among these, preferred are copolymers of acrylic acid or methacrylic acid with methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate. It will be done.

Polymer A used in the present invention is synthesized by a known method, and seven examples thereof include a backbone polymer having groups such as carboxylic acid, carboxylic acid halide, and carboxylic acid anhydride as side chains; A so-called polymer reaction is carried out by adding a reaction catalyst and a polymerization inhibitor and heating the compound represented by the general formula [1-al] under predetermined reaction conditions, so that a group having the general formula [1-al] in the side chain of the backbone polymer is added This is a method of introducing a group represented by I].

General formula [1-al [wherein R+ , , 1t 3 and X are represented by general formula [
I], and Y is 10H.

-3H, -NH-NHR (R is an alkyl group) or a halogen atom. ] Next, representative compounds represented by the general formula [1-al] that can be bonded to the group in the side chain of polymer A are as follows.

Allyl alcohol, 2-methylallyl alcohol, crotyl alcohol, 3-chloro-2-propen-1-ol, 3-phenyl-2-propen-1-ol, 3-(
hydroxyphenyl)-2-propen-1-ol, 3
-(2-hydroxyphenyl)-2-propen-1-ol, 3-(3,4-dihydroxyphenyl)-2-
Propen-1-ol, 3-(2,4-dihydroxyphenyl)-2-propen-1-ol, 3-(3,4
,5-trihydroxyphenyl)-2-propene-1-
ol, 3-(3-methoxy-4-hydroxyphenyl)-2-propen-1-ol, 3-(3,4-dihydroxy-5-methoxyphenyl)-2-propen-1
-ol, 3-(3,5-dimethoxy-4-hydroxyphenyl)-2-propen-1-ol, 3-(2-hydroxy-4-methylphenyl)-2-propen-1-
ol, 3-(4-methoxyphenyl)-2-propen-1-ol, 3-(4-ethoxyphenyl)-2-propen-1-ol, 3-(2-methoxyphenyl)-
2-propen-1-ol, 3-(3,4-dimethoxyphenyl)-2-propen-1-ol, 3-(3-
Methoxy-4-propoxyphenyl)-2-propene-
1-ol, 3-(2゜4.6-trimethoxyphenyl)-2-propen-1-ol, 3-(3-methoxy-
4-benzylphenyl)-2-propen-1-ol,
3- (3-(3'-methoxyphenyl)-4-benzyloxyphenyl)-2-propen-1-ol, 3-
Phenoxy-3-phenyl-2-propen-1-ol, 3-(3,4,5-trimethoxyphenyl)-2-
Propen-1-ol, 3-(4-methylphenyl)-
2-propen-1-ol, 3-phenyl-3-(2,
4,6-trimethylphenyl)-2-propen-1-ol, 3.3-[di(2,4,6-trimethylphenyl)]-]2-propen-1-ol 3-phenyl-3- (4-methylphenyl)-2-propene-1
-ol, 3,3-diphenyl-2-propen-1-ol, 3-(2-chlorophenyl)-2-propen-1
-ol, 3-(3-chlorophenyl)-2-propen-1-ol, 3-(4-chlorophenyl)-2-propen-1-ol, 3-(2,4-dichlorophenyl)
-2-propen-1-ol, 3-(2-bromphenyl)=2-propen-1-ol, 3-bromo-3-phenyl-2-propen-1-ol, 3-chloro-3-
Phenyl-2-propen-1-ol, 3-(4-nitrophenyl)-2-propen-1-ol, 3-(2-
nitrophenyl)-2-propen-1-ol, 3-(
3-nitrophenyl)-2-propen-1-ol, 2
-methyl 3-phenyl-2-propen-1-ol, 2
-Methyl-3-(4-chlorophenyl)-2-propen-1-ol, 2-methyl-3-(4-nitrophenyl)-2-propen-1-ol, 2-methyl-3-(4
-aminophenyl)-2-propen-1-ol, 2-
methylly, 3-diphenyl-2-propen-1-ol, 2-methyl-1,3-diphenyl-2-propen-1
-ol, 2-ethoxymethylene-3-phenyl-2-
Furopen-1-ol, 2-phenoxy-3-phenyl-2-propen-1-ol, 2-methyl-3-(4-
methoxyphenyl)-2-propen-1-ol, 2.
3-diphenyl-2-propen-1-ol, 1,2.
3-triphenyl-2-propen-1-ol, 2,3
．． 3-triphenyl-2-propen-1-ol, 2-
ethoxy-3-phenyl-2-propen-1-ol,
l, 3-diphenyl-2-propen-1-ol, 1-
(4-Methylphenyl)-3-phenyl-2-propen-1-ol, 1-phenyl-3-(4-methylphenyl)-2-propen-1-ol, 1-phenyl-3-
(4-methoxyphenyl)-2-propen-1-ol, 1-(4-methoxyphenyl)-3-phenyl-2-
Propen-1-ol, 1,3-di(4-chlorophenyl)-2-propen-1-ol, 1-(4-bromphenyl)-3-phenyl-2-propen-1-ol,
l-phenyl-3-(4-nitrophenyl)-2-propen-1-ol, 1,3-di(2-nitrophenyl)
-2-propen-1-ol, 1-(4-dimethylaminophenyl)-3-phenyl-2-propen-1-ol, 1-phenyl-3-(4-dimethylaminophenyl)-2-propen-1 -ol, 1,1-di(4-dimethylaminophenyl)-3-phenyl-2-propene-
1-ol, 1.1.3-triphenyl-2-propen-1-ol, 1,1,3.3-tetraphenyl-2
-propen-1-ol, 1-(4-methylphenyl)
-3-phenyl-2-propen-1-ol, 1-(dodecylsulfonyl)-3-phenyl-2-propen-1
-ol, 1-phenyl-2-propen-1-ol,
1,2-diphenyl-2-propen-1-ol, 1-
Phenyl-2-methyl-2-propen-1-ol, 1
-cyclohexyl-2-propen-1-ol, 1-phenoxy-2-propen-1-ol, 2-benzyl-
2-propen-1-ol, 1,1-di(4-chlorophenyl)-2-propen-1-ol,! -Carboxy 2-propen-1-ol, 1-carboxamide-
2-propen-1-ol, 1-cyano-2-propen-1-ol, l-sulfo-2-propen-1-ol, 2-ethoxy-2-propen-1-ol, 2-amino-2-ol Propen-1-ol, 3-(3-amino-4
-methoxyphenylsulfonyl)-2-propene-1-
All, 3-(4-methylphenylsulfonyl)-2-
Propen-1-ol, 3-phenylsulfonyl-2-
Propen-1-ol, 3-benzylsulfonyl-2-
Propen-1-ol, 3-anilinosulfonyl-2-
Propen-1-ol, 3-(4-methoxyanilinosulfonyl)-2-propen-1-ol, 3-anilino-2-propen-1-ol, 3-naphthylamino-2
-Propen-1-ol, 3-phenoxy-2-propen-1-ol, 3-(2-methylphenyl)-2-propen-1-ol, 3-(3-methylphenoxy)-
2-propen-1-ol, 3-(2,4-dimethylphenyl)-2-propen-1-ol,! -Methyl-3
-Carboxy-2-propen-1-ol, 3-carboxy-2-propen-1-ol, 3-bromo-3-carboxy-2-propen-1-ol, 1-carboxy-3-chloro-3-methyl- 2-Propen-1-ol, 1-carboxy-3-methyl-2-propen-1-ol, 1-(2-carbethoxyisoprobyl)-3-methyl-2-propen-1-ol, 1-( 1-carbethoxypropyl)-2-propen-1-ol, 1-(l
-carbethoxyethyl)-3-methyl-2-propene-
1-ol, 1-carbethoxy-3-chloro-3-methyl-2-propen-1-ol, 1-carbethoxymethylene-3-methyl-2-propen-1-ol, l-amide-2,3- dimethyl-2-propen-1-ol,
1-cyano-3-methyl-2-propen-1-ol,
3-sulfo-2-propen-1-ol, 3-butoxy-2-propen-1-ol, l-cyclohexyl-3
-(2-hydroxycyclohexyl) -2-propen-1-ol, 3-furyl-2-propen-1-ol, 3-chloro-2-propen-1-ol, 3-bromo-2-propen-1- ol, 2-methyl-3-bromo-2-propen-1-ol, 1-carboisobutoxy-3-chloro-3-methyl-2-propen-1-ol, 2-chloro-3-phenyl-2-ol Propen-1-ol (2-chlorocinnamyl alcohol), 2-bromo-
3-phenyl-2-propen-1-ol (2-bromocinnamyl alcohol), 2-bromo-3-(4-nitrophenyl)-2-propen-1-ol, 2-fluoro-3-phenyl-2 -propen-1-ol (2-fluorocinnamyl alcohol), 2-fluoro-3-(
4-methoxyphenyl)-2-propen-1-ol,
2-nitro-3-chloro-3-phenyl-2-propen-1-ol, 2-nitro-3-phenyl-2-propen-1-ol (2-nitrocinnamyl alcohol),
2-cyano-3-phenyl-2-propen-l-ol (2-cyanocinnamyl alcohol), 2-chloro-2
-Propen-1-ol (2-chloroallyl alcohol), 2-bromo-2-propen-1-ol (2-bromoallyl alcohol), 2-carboxy-2-propen-1-ol (2-carboxyallyl alcohol) ), 2
-carbetoxy-2-propen-1-ol (2-carbetoxyallyl alcohol), 2-sulfonic acid-2-propen-1-ol (2-sulfonic acid allyl alcohol), 2-nitro-2-propen-1- ol (2-nitroallyl alcohol), 2-bromo-3,3-difluoro-2-propen-1-ol, 2-chloro-3,3-ol
Difluoro-2-propen-1-ol, 2-fluoro-3-chloro-2-propen-1-ol, 2,3-dibromo-3-carboxy-2-propen-1-ol,
2.3-Short-3-carboxy-2-propene-1
-ol, 2,3-dibromo-2-propen-1-ol, 2-chloro-3-methyl-2-propen-1-ol, glycidyl acrylate, glycidyl methacrylate, and the like. Furthermore, in the above specific examples, compounds in which the alcohol at the 1st position is replaced with a thioalcohol, an amine, or a halogen can of course also be used.

A synthesis example of Polymer A is shown below.

Synthesis example (manufacture of copolymer of methacrylic acid and benzyl methacrylate) 300a equipped with a stirrer, reflux condenser and thermometer
+19.8g of poly(methacrylic acid/benzyl methacrylate = 27773 molar ratio) in a J2 three-necked flask
, 40.2 g of acetic acid ethylene glycol monomethyl ether as a reaction solvent, 6.0 g of allyl bromide as a reagent containing an unsaturated group, 10.4 g of trimethylbenzylammonium hydroxide as a catalyst, and 0.5 g of paramethoxyphenol as a polymerization inhibitor. Olg was added, mixed and dissolved, and heated and stirred at 70° C. for 13 hours under a nitrogen atmosphere. After cooling, methyl ethyl ketone is added to remove the liberated quaternary salt.

Further, methanol is added to dilute the mixture, and the mixture is poured into dilute hydrochloric acid to precipitate. After washing the precipitate with water, the precipitate was suction filtered and vacuum dried to obtain a polymer in a yield of 13.6 g. An example of synthesis in which the allyl group is introduced into a copolymer of carboxylic acid or maleic anhydride as a backbone polymer is shown in U.S. Pat.
, 047,398, whereby the maleic anhydride moiety is ring-opened and unsaturated esters, amides, thioesters, etc. are introduced.

(B) Photopolymerization initiator The photopolymerization initiator used in the present invention as component (B) includes those conventionally used in this technical field, but the following are preferred. can be used.

Benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy α-phenylacetophenone, benzophenone, 2.4-
Benzophenone derivatives such as dichlorobenzophenone, methyl 0-benzoylbenzoate, 4,4"-bis(dimethylamino)benzophenone, 4.4"-bis(diethylamino)benzophenone, 2-chlorothioxanthone,
Thioxanthone derivatives such as 2-isopropylthioxanthone, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α.

α-jethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound, halogen compound, etc.

In addition, vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2.387.660, U.S. Pat.
α-carbonyl compounds disclosed in No. 367.861 and No. 2,367.670, No. 2,44
Asiloin ether disclosed in No. 8,828, α-hydrocarbon-substituted aromatic acyloin compound disclosed in No. 2,722,512, No. 3,046,127 Polynuclear quinone compounds disclosed in No. 3 and No. 2,951,758;
The triarylimidazole dimer/p-aminophenyl ketone combination disclosed in No. 49,367, the benzothiazole compound disclosed in No. 3,870,524, and the benzothiazole compound disclosed in No. 4.239. Benzothiazole compounds/triheromethyl-8-triazine compounds disclosed in No. 850 and No. 3.7 of the same
Acridine and phenazine compounds disclosed in Specification No. 51,259, oxadiazole compounds disclosed in Specification No. 4,212.970, etc.

The amount of these photopolymerization initiators used is about 0.5% to about 15% by weight, preferably 2% to 10% by weight, based on the total weight of the components constituting the photosensitive layer.

It is preferable to further add a thermal polymerization inhibitor to the photosensitive layer used in the present invention, such as hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2'-methylenebis(4-methyl −
6-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

(c) Diazo resin The diazo resin which is the component (c) used in the present invention has been conventionally used in negative planographic printing plate materials, and specifically, it is a diazo resin that is a diazo monomer and a condensing agent such as an aldehyde. A reaction product of a condensate obtained by condensing a molar ratio of 1:1 to 1:0.5, preferably 1:0.8 to 1:0.6 in a conventional manner and an anion. It is.

Examples of the diazo monomer include 4-diazo-diphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, l-diazo-4-N, N-diethylaminobenzene, and l-diazo-4-N-ethyl- N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-
N-hydroxyethylaminobenzene, 1-diazo-2
, 5-jethoxy-4-benzoylaminobenzene, l
-Diazo-4-N-benzylaminobenzene, l-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p-tolylmercapto Benzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazodimethylaniline, l-diazo-2,
5-dibutoxy-4-morpholinobenzene, l-diazo-2,5-jethoxy-4-morpholinobenzene, l-
Diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-jethoxy-4-p-tolylmercaptobenzene, l-diazo-4-N-ethyl-N-
Hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, l-diazo-3-chloro-4-N, N-diethylaminobenzene, 1-diazo-3-methyl- 4-pyrrolidinobenzene, l-diazo-2-chloro-4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-
Methoxy-4-pyrrolidinobenzene, 3-methoxy-4
-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3-(n-propoxy)-4-diazodiphenylamine, 3-(isopropoxy)-4-diazodiphenylamine, and the like.

Examples of the aldehyde used as a condensing agent with the diazo monomer include formaldehyde, adetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde.

Furthermore, water-soluble diazo resins can be obtained by using chloride ions, tetrachlorozinc acid, etc. as anions, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4,4° -biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid,
By using 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc., an organic solvent-soluble diazo resin can be obtained.

The amount of the diazo resin constituting the photosensitive layer used in the present invention is 1% based on the total weight of the components constituting the photosensitive layer.
Weight% to 30% by weight, preferably 5% to 20% by weight
Weight%.

The photosensitive layer used in the present invention mainly contains the above-mentioned components (A), (B) and (c), but may further contain unsaturated additives as described below.

Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol and dipentaerythritol Tri, tetra or hexa(meth)acrylate, epoxy di(meth)acrylate, oligoacrylate as disclosed in Japanese Patent Publication No. 52-7361, acrylic urethane resin or acrylic as disclosed in Japanese Patent Publication No. 48-41708 These include urethane oligomers.

The composition ratio of these monomers or oligomers to the (A) polymer is preferably in the range of 1:9 to 7:3 by weight, and more preferably in the range of 1:3 to 1:1 by weight.

The addition amount of the photopolymerization initiator constituting the photosensitive layer used in the present invention is based on the total weight of the components constituting the photosensitive layer.
About 0.5% to about 15% by weight, preferably 2% to 10% by weight.

Furthermore, a binder can be added to the photosensitive layer used in the present invention, if necessary. Various polymeric compounds can be used as the preferred binder, but monomers having aromatic hydroxyl groups such as those described in JP-A No. 54-98613, such as N-(4-hydroxy Copolymers of phenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, 0-1m-1 or p-hydroxystyrene, 0-1l-1 or p-hydroxyphenyl methacrylate and other monomers, Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in U.S. Pat. No. 4,123.276; Natural resins such as shellac and rosin; polyvinyl alcohol; 3.751,25
Polyamide resins as described in No. 7,
Linear polyurethane resins, polyvinyl alcohol phthalate resins, epoxy resins condensed from bisphenol A and epichlorohydrin, cellulose acetate, cellulose acetate phthalate, etc. as described in U.S. Pat. No. 3,660,097. Includes celluloses.

The components constituting the photosensitive layer used in the present invention are, for example,
A suitable solvent such as 2-methoxyethanol, 2-methoxyethyl acetate, cyclohexane, methyl ethyl ketone, ethylene dichloride, etc. or a solvent used as a developer as described below is dissolved alone or in a suitable mixture of these solvents and applied onto a support. coated.

Furthermore, in addition to the above, the photosensitive layer contains dyes (for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue '603) to make the image visible after exposure or development.
(Triphenylmethane-based and diphenylmethane-based dyes such as (manufactured by Orient Kagaku Kogyo Co., Ltd.)), alkyl ethers to improve coating properties (e.g., ethyl cellulose, methyl cellulose, etc.), fluorine-based surfactants, nonionic surfactants (For example, Pluronic L64 (manufactured by Laiseika Co., Ltd.)
etc.), plasticizers to impart flexibility to the coating film (e.g.
polyethylene glycol, tricresyl phosphate, acrylic acid or methacrylic acid polymers, etc.), stabilizers (for example, phosphoric acid, oxalic acid, tartaric acid, etc.).

The fluororesin layer used in the present invention acts as an ink repellent layer, and the fluororesin used for the core layer contains a copolymer resin of perfluoroalkyl methacrylate and glycidyl methacrylate in the molecule of the fluororesin. (The content of fluorine is 30% by weight or more, preferably 50% by weight or more), or (1) CF3-5-CF2- -CF-1CF3-0- is present in the molecule of the fluororesin. 1-C
F2-0-1-CF-0- (Fluorine content is 30% by weight
(preferably 50% by weight or more), and (2) a functional group that can react with a crosslinking agent in the molecule of the fluororesin, or a functional group that can crosslink with each other as described below. used.

Specifically, the following polymers are exemplified.

■An acrylate containing a copolymer resin of perfluoroalkyl methacrylate and an acrylic monomer having a hydroxyl group, such as 2-hydroxyethyl methacrylate;
-Methacryloyloxyethyl copolymer resin The fluororesin used in the present invention is preferably a copolymer resin of a fluorine-containing acrylic monomer and a fluorine having a functional group capable of reacting with a crosslinking agent.

As the fluorine-containing acrylic monomer, a compound having the following general formula is preferable.

In the formula, Rf is a substituted fluorine alkyl group or a substituted fluorine polyether group, and R is a hydrogen atom or an alkyl group.

Preferred examples of the fluorine-containing acrylic monomer include the following monomers.

Examples of monomers having functional groups that can react with crosslinking agents include glycidyl methacrylate, methacrylic acid,
Examples include 2-hydroxy methacrylate.

The fluorine-containing resin used in the present invention is a copolymer resin of the above-mentioned fluorine-containing acrylic monomer and a copolymer having a functional group that can react with a crosslinking agent, and a third copolymer having a copolymer having a functional group that can react with a crosslinking agent. - is also preferably copolymerized. Examples of the third polymer include styrene, methyl methacrylate (MM^), butyl acrylate, acrylonitrile, and ethyl acrylate.

The fluororesin of the present invention is -0H1-COOH, -NH2,
When it has an active hydrogen functional group such as -NH-, a compound having two or more functional groups capable of reacting with active hydrogen such as -CH-CH2 and -NCO in its molecule is preferably used as a crosslinking agent. Specifically, the following compounds are exemplified.

(1) Hexamethylene diisocyanate (4) Bisphenol A diglycidyl ether In addition, the fluororesin of the present invention is CH-Ch, ~NC
When it has a functional group that can react with active hydrogen such as O,
Compounds having active hydrogen functional groups such as -0H1-COOH5-NH2, -NH-, or acid anhydrides (eg, pentaerythritol, diethylenetriamine, hexahydrophthalic anhydride) can be used as crosslinking agents. Further, the fluororesin of the present invention has a group or -0H1-COOHl-N)I2
．． -N)I- or a group derived from an acid anhydride (e.g., pentaerythritol, diethylenetriamine, hexahydrophthalic anhydride), directly or via a crosslinking agent. Can react with components of the photosensitive layer.

When the fluororesin of the present invention has both an active hydrogen functional group and a functional group that can react with active hydrogen, or a fluororesin that has an active hydrogen functional group and a fluororesin that has a functional group that can react with active hydrogen are mixed. When used as a cross-linking agent, a cross-linking agent may not be used.

The amount of the fluororesin used in the fluororesin layer of the present invention is 60 to 100% by weight, preferably 80 to 9% by weight.
Very effective at 8% by weight.

The fluororesin layer of the present invention is formed by dissolving a fluororesin and a crosslinking agent in a suitable solvent, coating the photosensitive layer, drying, and crosslinking the fluororesin by heat treatment.

In the present invention, in addition to the above-mentioned components, a small amount of a crosslinking reaction catalyst such as a tin compound such as dibutyltin laurate, a quaternary or tertiary amine compound such as triethylbenzylammonium chloride, benzyldimethylamine, etc. is contained. be able to.

The support used in the plate material of the present invention is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metals such as aluminum, minilum, zinc, copper, and steel. Examples include metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic films and glass plates, resin coated paper, paper covered with metal foil such as aluminum, etc. .

Among these, aluminum plates are preferred.

The treatment for the support itself to improve the adhesion is not particularly limited, and includes various surface roughening treatments.

In addition, before coating the photosensitive layer on the support, a brimer layer may be provided on the support in order to obtain sufficient adhesion between the photosensitive layer and the support. -vinyl acetate copolymer, acrylic resin,
Examples include vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

In addition, as the anchor agent constituting the above-mentioned brimer layer,
For example, silane coupling agents, silicone primers, etc. can be used, and organic titanates and the like are also effective.

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support has a thickness of 50 to 400 μm, preferably 10
0-300 pm, the photosensitive layer is O, (15-10 μm,
Preferably 0.5 to 5 μm, and the fluororesin layer has a thickness of 0.01 to 1
It is 0 μm, preferably 0.1 to 1 μm.

In the present invention, a protective layer may be provided on the upper surface of the fluororesin layer, if necessary.

The lithographic printing plate material V which does not require dampening water of the present invention can be manufactured, for example, as follows.

A composition solution to form a photosensitive layer is coated onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coater such as a Whaler, and then dried and heated if necessary. I'm curious.

If necessary, a brimer layer may be provided between the support and the photosensitive layer in the same manner as in the case of the photosensitive layer. Next, a fluororesin and a crosslinking agent are coated on the photosensitive layer in the same manner, and usually 1.
A heat treatment is performed at a temperature of 00 to 120° C. for several minutes to fully cure and form a fluororesin layer. If necessary, a protective film can be provided on the fluororesin layer using a laminator.

Next, a method for producing a lithographic printing plate that does not require dampening water using the lithographic printing plate material that does not require dampening water of the present invention will be described.

A positive film, which is the manuscript, is vacuum-adhered to the surface of the positive plate material and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used.

Next, the positive film is peeled off and developed using a developer. As the developer, any known developer for lithographic printing plates that does not require dampening water can be used. For example, aliphatic hydrocarbons (
Hexane, heptane, "Isopar E, H, G" (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), or halogens. Preferably, the following polar solvents are added to hydrogenated hydrocarbons (such as tricrene).

Alcohols (methanol, ethanol, water, etc.), ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carpitol, ethyl carpitol, butyl carpitol, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters ( (ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) It is also possible to dye the image area at the same time as development by adding a dye such as crystal violet or astrazonelet to the developer.

Development can be carried out by a known method, such as rubbing with a developing pad containing a developer as described above, or pouring a developer onto the printing plate and then rubbing with a developing brush.

By the above development, the fluororesin in the unexposed areas is removed and the photosensitive layer is exposed, and a printing plate is obtained in which the fluororesin layer remains in the exposed areas.

[Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 On a degreased aluminum plate with a thickness of 0.24no++,
A primer layer having the following composition was applied and cured at 150° C. for 3 minutes to form a 2 μm thick primer layer.

[Composition of primer layer] Epikote 1001 (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A-based epoxy resin) 50 parts Ebomate 5002 (manufactured by Yuka Shell Epoxy Co., Ltd., hardening agent) 50 parts Toluene
400 parts methyl cellosolve 400 parts Photosensitive composition-1 having the following composition was coated on the brimer layer and dried at 100° C. for 3 minutes to form a 2 μm thick photosensitive layer.

[Photosensitive composition-1] (1) 120 parts of condensate of P-diazophenylamine hexafluorophosphate and formaldehyde (2) Copolymerization of methacrylic acid produced in the synthesis example and benzyl methacrylate Resin 80 parts (3) 30 parts (1:4) condensate of xylene diamine and glycidyl methacrylate (4) Benzophenone 8 parts (5
) Methyljetanolamine 9 parts (6) Hydroquinone 0.5 part Next, after coating the surface of the photosensitive layer with fluororesin composition-1 having the composition below, the core layer was cured at 120°C for 5 minutes. A cured fluororesin layer with a thickness of 1.0 μm was formed.

[Fluororesin composition-1] (1) IH, IH, 21(,2H-heptadecafluorodecyl methacrylate [CH, -C(cH3) CO
O(c)12) 2 (cF2) aF], 2-hydroxyethyl methacrylate, methyl methacrylate, 40 parts of a copolymer resin with a molar ratio of 70.20.10 (
2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 2 parts (3) Dibutyltin dilaurate 0.05 part (4) Freon-11
3200 parts (5) 0-xylene hexafluoride 20 parts A layer of 12 μm thick was applied to the surface of the fluororesin layer obtained as above.
A lithographic printing plate material that does not require dampening water was obtained by laminating a polyethylene terephthalate film with one side matted.

After a positive film was vacuum-adhered to the upper surface of the above plate material, it was exposed to light for 10 seconds using a metal highland lamp as a light source.

Next, the laminate film was peeled off from the surface of the exposed plate material and developed using the following developer. During development, by rubbing the surface of the plate material with a development bat (sponge),
Only the unexposed portions of the fluororesin layer were easily removed. A lithographic printing plate was obtained in which the fluororesin layer in the exposed areas was firmly adhered and did not require dampening water.

[Developer Composition-11 Isopar) 1 70 parts Toluene 3 parts Turfitz (manufactured by Clarei Soprene Chemical Co., Ltd.) 27 parts Next, the above printing plate was placed in a Heidenberg GT with the dampening water supply device removed.
Attached to O printing machine, manufactured by Osaka Ink Manufacturing Co., Ltd., OPI W
When printed using LP PROCESS W RED H, 20,000 prints with good small dot reproducibility and shadow part reproducibility were obtained.

Example 2 A plate material was prepared in the same manner as in Example 1 except that fluororesin composition-1 of Example 1 was changed to fluororesin composition-2 having the following composition, exposed for 8 seconds, and then developed. and obtained the printed version.

In this printing plate, the fluororesin layer in the exposed area was firmly adhered, and when printed in the same manner as in Example 1, 20,000 prints with good dot reproducibility and shadow area reproducibility were obtained. .

[Fluororesin composition-2] 40 parts of copolymer resin with a molar ratio of 70.20 and 1O (
3) Dibutyltin dilaurate 0.05 parts (4)
Freon-113, 200 parts (5) a+-xylene hexafluoride 50 parts Comparative Example A lithographic printing plate material was prepared according to the method of Example 1, except that no diazo resin was added as a photosensitive layer. Similarly, this plate material was exposed to light for 20 seconds and then developed to obtain a printing plate. When printing was performed using this plate, streak-like stains were observed over the entire plate surface as the amount of printing increased.

Furthermore, in developing the plate material, Examples 1 and 2 were able to be developed even by scrubbing the exposed plate material with a sponge, but in the comparative example, the fluororesin in the shadow area was removed by rubbing several times with force. , it peeled off.

In the above examples, "parts" means "parts by weight" unless otherwise specified.

[Effects of the Invention] In the present invention, since a strong bond is formed between the photosensitive layer and the fluororesin layer, the resulting lithographic printing plate material that does not require dampening water has a wide development latitude and is highly movable. The printing plate obtained by developing the plate material using the printing plate has excellent rigidity resistance, excellent reproducibility of shadow areas and small dots, and has the excellent effect of not causing scumming on the plate surface. .

Furthermore, the plate material of the present invention has the advantage that a developer using a solvent other than fluorine can be used.

Applicant: 1 person other than Co., Ltd. Representative patent attorney: Miki Nakashima, Yugai (1 person)

Claims (1)

[Claims] In a lithographic printing plate material that does not require dampening water and has a photosensitive layer and a fluororesin layer in this order on a support, the photosensitive layer contains (A) an ethylenically unsaturated addition polymerization compound, (B) a photopolymerization initiator, and (c) ) A lithographic printing plate material that does not require dampening water and is characterized by containing a diazo resin.