JPH02273748A - Damping-waterless planographic printing plate - Google Patents

Abstract

PURPOSE:To form the printing plate having excellent plate wear and image reproducibility by incorporating a specific diazo resin as a photosensitive material into a photosensitive layer. CONSTITUTION:The photosensitive layer contains the diazo resin having the repeating unit expressed by formula I as the photosensitive material and an ink repulsion layer is formed of a fluoroplastic layer and silicone rubber layer. In the formula I, A denotes a residual group of an arom. diazonium compd. which can be condensed with formaldehyde; B denotes a residual group of an arom. compd. having at least either or both of one carboxyl group and at least one hydroxyl group. X denotes diazo anion; Y denotes an intermediate link derived from a condensable carbonyl group; m and n denote 1 to 200 integer. The printing plate having the excellent plate wear and image reproducibility is formed in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a lithographic printing plate material that does not require dampening water, and more specifically, a planographic printing plate material that has excellent image reproducibility and good printing durability when used for printing. This invention relates to a lithographic printing plate material that does not require dampening water and can form a lithographic printing plate. [Background of the Invention] Conventionally, as a lithographic printing plate material that does not require dampening water (hereinafter also simply referred to as "plate material" for short), It is known that a photosensitive layer and an ink-repellent layer are coated on a support in order from the support side, and by exposing and developing this plate material, a lithographic printing plate that does not require dampening water (hereinafter referred to as (also simply referred to as a "printed version" for short) is obtained.

A technique using fluororesin as a material for forming the rationality of the ink roll is known, for example, in Japanese Patent Application Laid-Open No. 58-21
Publication No. 5411 discloses a plate material in which a fluorine-containing copolymer formed from a specific fluorine-containing acrylic monomer and a monomer having a photosensitive group is used as an ink-repellent layer.

However, the printing plate obtained from this plate material has the drawbacks of insufficient rigidity (and poor reproducibility of shadow areas and small dots). If the content of photosensitive groups in the plate material is increased in an attempt to improve the printing properties, the ink repellency of the resulting printing plate decreases and scumming tends to occur.

In addition, in the conventional plate material in which a photosensitive layer and a fluororesin layer are coated on a support in order from the support side, the adhesion between the photosensitive layer and the fluororesin layer is insufficient, and no image is formed during development. It has the disadvantage that the fluororesin layer in the line portion is easily peeled off and the development latitude is narrow. Therefore, in order to improve the adhesion between the photosensitive layer and the fluororesin layer in such a plate material, for example, perfluoroalkyl having a metal atom and a functional group bonded to the metal atom in the ink repellent layer can be used. A plate material using an ink repellent layer formed from a compound is disclosed in WO 33-02175, and in this plate material, the adhesion can be improved by the presence of metal atoms, and the thickness of the ink repellent layer can be increased by 10%. The printing plate obtained from this plate material is
Although this printing plate is characterized by high resolution, it also has insufficient rigidity resistance, and streaks of stain occur over the entire plate surface.

On the other hand, a technique using silicone rubber as a material constituting the above-mentioned ink anti-I rationality is also known (for example, see Japanese Patent Application Laid-open Nos. 48-94504, 50-59103, and 55-55343). Since it is originally difficult to obtain sufficient adhesion between this silicone rubber layer and the photosensitive layer, plate materials using this silicone rubber layer as a repulsion layer cannot form printing plates with sufficient rigidity resistance. Moreover, when such a plate material is stored for a long time, the adhesive strength further decreases, and there is a problem that a printing plate that produces a good image cannot be obtained.

Therefore, the inventors of the present invention have conducted various studies in view of the above-mentioned situation, and have developed a method that does not require dampening water and is made by laminating a photosensitive layer and an ink anti-ta layer on a support in order from the support side. In the lithographic printing plate material, when the photosensitive layer contains a photosensitive diazo resin having a repeating unit represented by the following general formula (2), such a photosensitive layer and an ink repellent layer made of a fluororesin or silicone rubber can be combined. We have discovered that it is possible to form a printing plate that has improved stiffness by improving the adhesion between the two, and also has good image reproducibility.

General formula I N, Represents a residue of a diazonium compound, B is
X represents a diazo anion, Y represents an intermediate link derived from a condensable carbonyl compound, and m and n each represent 1
Represents an integer between ~200.

[Object and structure of the invention]

The present invention was invented based on the above findings, and aims to provide a lithographic printing plate material that does not require dampening water and can form a printing plate with excellent stiffness resistance and image reproducibility. In this lithographic printing plate material that does not require dampening water and is formed by laminating a photosensitive layer and an ink repellent layer in order from the support side, the photosensitive layer has the following general formula! Contains a diazo resin having a repeating unit represented by as a photosensitive substance,
and a lithographic printing plate material that does not require dampening water, characterized in that the ink repellent layer is formed from a fluororesin layer or a silicone rubber layer, and the general formula: ■ zX 1←A−Y+−(−B−Y+− [In the formula, A represents a residue of an aromatic diazonium compound that can be condensed with formaldehyde, provided that A represents two or more residues that are the same or different, and B is the same or different, or a residue of an aromatic compound having one or both of at least one carboxyl group and at least one hydroxyl group, provided that it represents two or more different types of residues, and X represents a diazo anion. , Y represents an intermediate link derived from a condensable carbonyl compound, and m and n each represent an integer from 1 to 200].

[Detailed description of the invention]

The present invention will be explained in more detail below.

The plate material of the present invention contains in the photosensitive layer a diazo resin having a repeating unit represented by the above-mentioned hole (■). and an aromatic compound having one or both of at least one carboxyl group and at least one hydroxyl group (hereinafter also collectively referred to as "aromatic compound"). , said - A and B in the hole I
represent the residues of these aromatic diazonium compounds and aromatic compounds, respectively.

The aromatic diazonium compound that produces the residue represented by A is not particularly limited as long as the diazonium group is directly bonded to the aromatic ring (
Examples include 4-diazodiphenylamine sulfate, 4
-Diazodiphenylamine tetrafluoroborate, 4-diazodiphenylamine hexafluorophosphate, 4-morpholino-
Benzenediazonium tetrafluoroborate, 4-(N-ethyl-N-hydroxyethyl)-aminobenzenediazonium sulfate, 4-N,N'-dimethylaminobenzenediazonium hexafluorophosphate, and 8-hydroxy- 2-
naphthalenediazonium tetrafluoroborate, 4-diazo-
4'-Methoxydiphenylamine hexafluorophosphate, 4
-Diazo-4'-methoxyphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-diazo-4'-ethoxydiphenylamine hexafluorophosphate, 4-diazo-4'-propoxydiphenylamine・Tetrafluoroborate, 3-methoxy-4-morpholino-benzenediazonium ・Hexafluorophosphate, 3
-Methoxy-4-N,N'-dimethylaminobenzenedidizonium tetrafluoroborate, 4-diazo-3-methoxydiphenylamine hexafluorophosphate, 4-diazo-3-methoxytetrafluoride Examples include borates and 8-methoxy-2-naphthalenediazonium hexafluorophosphates. Among these, particularly preferred aromatic diazo compounds include:
4-Diazo-4'-methoxydiphenylamine salt, 4-
Diazo-4'-ethoxydiphenylamine salt and 4-
Diazo-3-methoxydiphenylamine salt is mentioned.

The aromatic compound producing the residue represented by B contains in its molecule an aromatic ring substituted with at least one carboxyl group and/or at least one hydroxyl group, and these When there are two or more carboxyl groups and two or more hydroxyl groups, these substituents may be bonded to the same aromatic ring or may be bonded to separate aromatic rings.

Preferable examples of the aromatic ring include aryl groups, such as phenyl and naphthyl groups.

The above carboxyl group and hydroxyl group may be bonded directly to the aromatic ring or may be bonded via a joint.

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 preferably 1 to 3. Furthermore, examples of the joint include an alkylene group having 1 to 4 carbon atoms.

In order to condense the aromatic compound with aldehydes or ketones, it is necessary to have at least two unsubstituted sites on the aromatic ring of one or more aryl groups substituted with at least one hydroxyl group. is necessary.

Specific examples of aromatic compounds having at least one carboxyl group in the molecule include benzoic acid, 2-fluorobenzoic acid, 2-naphthoic acid, p-methoxybenzoic acid, 2.
4-dimethoxybenzoic acid, 2,4-'; methylbenzoic acid, p-phenoxybenzoic acid, p-methoxyphenylacetic acid, 4-anilinobenzoic acid, 4-(m-methoxyanilino)benzoic acid, 4-(p -methoxybenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, etc. Among these, particularly preferred are 2,4-dimethoxybenzoic acid,
p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4-
(m-methoxyanilino)benzoic acid and 4-(p-methylanilino)benzoic acid.

Specific examples of aromatic compounds having at least one hydroxyl group in the molecule include phenol, (o.

m, p) Cresol, xylenol, resorcinol, 2-
Methylresorcin, (o=p9m)methoxyphenol, m-ethoxyphenol, catechol, phloroglucin, P-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl4.
4'-diol, 1.2.4-benzenetriol, bisphenol A, 2.4-dihydroxybenzophenone, 2°3.4-1-dihydroxybenzophenone, p-
Hydroxyacetophenone, 4.4-dihydroxydiphenyl ether, 4.4'-dihydroxydiphenylamine, 4.4'-dihydroxysulfone, 4.4'
-dihydroxydiphenyl sulfide, cumylphenol, etc., and particularly preferred among these are p
-cresol, resorcin, 2-methylresorcin, pyrogallol, P-methoxyphenol, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylamine, 2,3,4-)dihydroxybenzophenone.

Specific examples of aromatic compounds having both a carboxyl group and a hydroxyl group in the molecule include salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, and 6-salicylic acid. Thiarylinaricylic 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-dihydro-1-
cy-6-methylbenzoic acid, 2,6-dihydroxybenzoic acid, 2,6-cyhydroxy-4-methylbenzoic acid, 4-
Chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2°4.5-)dihydroxybenzoic acid,
m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p-)ruyl) gallic acid, protocatechol-gallic acid, 4,6-cyhydroxyphthalic acid, (2
,4-dihydroxyphenyl)acetic acid, (2゜6-dihydroxyphenyl)acetic acid tL (3,4,5trihydroxyphenyl)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, 4-(p-hydroxyanilino)benzoic acid, bis(3-carboxy-4-hydroxyphenyl)amine,
4-(p-hydroxyphenylsulfonyl)benzoic acid,
Examples include 4-(p-hydroxyphenylthio)benzoic acid, and among these, salicylic acid and p-
Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid,
Gallic acid, phloroglucin carboxylic acid, and 4-(p
-hydroxyanilino)benzoic acid.

Examples of the aldeside and ketone used as a cocondensation component in producing the photosensitive diazo cocondensation resin used in the present invention include paraformaldehyde, acetaldehyde, benzaldehyde, or ketones;
For example, acetone, acetophenone,
Among them, paraformaldehyde is preferably used.

Therefore, these aldehydes and ketones, after condensation, form an intermediate link, denoted by Y in said hole I, and combine with said residues A and B to form an intermediate link in said hole I. The blocks represented by -(-A-Y→T and -←B-Y+r are formed, and m and n in these blocks generally represent an integer of 1 to 200, preferably an integer of 2 to 20.

The photosensitive diazo co-condensed resin can be prepared by a known method, for example,
Photographic Science and Engineering, Volume 17, Page 33 (1973), U.S. Patent No. 2,063
．． 631 and 2.679.498, an aromatic diazonium compound, an aromatic compound containing either or both of a hydroxyl group and a hydroxyl group, and aldehydes in sulfuric acid, phosphoric acid or hydrochloric acid; For example, it can be obtained by polycondensing paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenine.

Furthermore, these aromatic diazonium compounds, aromatic compounds containing either or both of a hydroxyl group and a carboxyl group, aldehydes, and ketones may of course be combined with each other in any manner (furthermore, each of these components may be More than one type can be used in combination, and therefore, not only the residues A and B in the symbol (-), but also Y may be two or more different groups.

When condensing an aromatic diazonium compound, an aromatic compound, and an aldehyde and/or ketone as described above, the molar ratio of the aromatic diazonium compound to the aromatic compound is generally 0.1:I to 1:0.1, preferably is 0.2:1 to 1:0.5, more preferably 0.2:1
~1:1, and the charging molar ratio of the sum of aromatic diazonium compound and aromatic compound to the sum of aldehyde and ketone is generally 1:0.6 to 1:2, preferably 1:0.
．． 7 to 1:1.5, and a diazo cocondensation resin can be obtained by reacting these components at low temperature for a short time, for example, about 3 hours.

The diazo anion of the diazo resin used in the present invention, i.e., ing. Such anions include organic carboxylic acids such as decanoic acid and benzoic acid;
Contains organic phosphoric acids such as phenyl phosphoric acid and sulfonic acids,
Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, Aliphatic and aromatic sulfonic acids such as hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5-sulfoisophthalate, 2.2', 4.4'-tetrahydroxybenzophenone, 1.2.3-) Hydroxyl group-containing aromatic compounds such as hydroxybenzophenone, 2,2',4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, C1O,,1
Examples include various anions such as perhalogen acids such as 0, etc., and among these, particularly preferred is an anion of hexafluorophosphoric acid.

The condensation type diazo resin with the aromatic diazonium compound used in the present invention and an aldehyde and/or ketone containing the aromatic compound as a constituent unit, in other words, the diazo resin having the repeating unit represented by the above-mentioned crest I. Examples include 4-diazodiphenylamine salicylate/hexafluorophosphate-formaldehyde resin, 4-methylsalicylic acid-4-diazodiphenylamine/tetrafluoroborate-formaldehyde resin, and 4-diazodiphenylamine p-hydroxybenzoate.・Hexafluorophosphate-formaldehyde resin, 2,4-dihydroxybenzoic acid-4
-diazodiphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate-formaldehyde resin, gallic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, phloroglucincarboxylic acid-4-diazodiphenylamine Tetrafluoroborate-acetaldehyde resin, (2,4-dihydroxyphenyl) acetic acid m-4-(N-c-f-N-hydroxyethyl)-aminobenzenediazonium hexafluorophosphate-benzaldehyde resin, 4-(0-hydroxybenzoyl)benzoic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, 4-(p-hydroxyphenoxy)benzoic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, 4-(p-
Hydroxyanilino)benzoic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde m fat, 4
(p-hydroxyphenylsulfonyl)benzoic acid-4-
Diazodiphenylamine/hexafluorophosphate-formaldehyde resin, salicylic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 4-methylsalicylic acid-4-diazo-4'-methoxydiphenylamine hexafluoride Phosphate-formaldehyde resin, P-hydroxybenzoic acid-4-diazo-4'
-Methoxydiphenylamine/hexafluorophosphate -formaldehyde resin, p-hydroxybenzoic acid-4-diazo-3-methoxydiphenylamine/hexafluorophosphate -formaldehyde resin, gallic acid-4-diazo-4'
-Ethoxydiphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate-formaldehyde resin, 4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 4.
4'-dihydroxydiphenylamine-4-diazo-4
'-Ethoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 2゜4-dimethoxybenzoic acid-4
-Diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 4-anilinobenzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorosulfate-formaldehyde tree IL p-phenoxybenzoic acid -4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 2
．． 4-Dihydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 4-(p-hydroxyanilino)benzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate phosphate-formaldehyde resin, p-cresol-4-diazo-3-methoxydiphenylamine/hexafluorophosphate-benzaldehyde resin, resorcin-4-
Diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 2-methylresorcin-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, pyrogallol-
4-Diazo-3-methoxydiphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate-formaldehyde resin, pyrogallol-4-diazo-41-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 2° Examples include 4-dihydroxybenzophenone-4-diazo-4'-ethoxydiphenylamine/hexafluorophosphate-formaldehyde resin; particularly preferred among these are 4-diazodiphenylamine salicylate/hexafluorophosphate-formaldehyde resin. , p-hydroxybenzoic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, 2.4
-Dihydroxybenzoic acid-4-diazodiphenylamine/2-hydroxy-4-methoxybenzophenone-5-
sulfonate-formaldehyde resin, and 4-(p
-Hydroxyanilino)benzoic acid -4-diazodiphenylamine/hexafluorophosphate -formaldehyde resin, salicylic acid -4-diazo-4'-methoxydiphenylamine/hexafluorophosphate -formaldehyde resin, p-hydroxybenzoic acid- 4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin,
2.4-dihydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, resorcin-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, Pyrogallol-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 2,4-dihydroxybenzophenone-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, etc. , a formaldehyde resin in which an aromatic compound having both a carboxyl group and a hydroxyl group in the molecule and an aromatic diazo compound are co-condensed, and more preferred are 4-diazodiphenylamine salt, 4-diazo compound as the aromatic diazo compound. Diazo-4'
-methoxydiphenylamine salt, 4-diazo-4'-ethoxyamine salt and 4-diazo-3-methoxydiphenylamine salt.

The molecular weight of the diazo resin can be changed as appropriate by selecting the relative molar ratio of each monomer charged and the condensation conditions, but for the purpose of the present invention, the molecular weight is generally about 400 to 10.000. Suitably, it is preferably about 800 to 5,000.

Next, typical synthesis examples of these diazo resins will be shown.

Synthesis of Diazo Resin 1 3.5 g (0,025 mol) of p-hydroxybenzoic acid and 22.0 g (0,075 mol) of 4-diazo-4'-methoxydiphenylamine sulfate were mixed under water cooling with 9
Dissolved in 0g of concentrated sulfuric acid. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) were added slowly. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was poured into 11 ethanol under water cooling, and the resulting precipitate was filtered.

After washing with ethanol, this precipitate was dissolved in 200 mf of pure water, and to this solution was added a cold concentrated aqueous solution in which 10.5 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and dissolved in 300 mf pure water. A cold concentrated aqueous solution containing 13.7 g of ammonium hexafluorophosphate was added to this solution. The resulting precipitate was filtered, washed with water, and then dried at 30°C for one day and night to obtain diazo cocondensation resin 1.

When the molecular weight of this diazo cocondensation resin-1 was measured by GPC, the weight average molecular weight was about 2.300.

Synthesis of Diazo Resin 2 3.5 g (25 mmol) of p-hydroxybenzoic acid and 21.75 g (7 mmol) of P-diazodiphenylamine sulfate
5 mmol) was dissolved in 90 g of concentrated sulfuric acid under water cooling.

To this solution, 2.7 g (90 mmol) of paraformaldehyde was slowly added. At this time, the reaction temperature was 10
The temperature was added so as not to exceed °C. After stirring the reaction solution for 2 hours, it was added dropwise to 12 ethanol, and the resulting precipitate was filtered out and washed with ethanol. The precipitate was dissolved in 200 mf of pure water, and an aqueous solution containing 10.5 g of zinc chloride was added.

After filtering the resulting precipitate and washing with ethanol,
It was dissolved in ml of pure water. To this solution was added an aqueous solution containing 13.7 g of ammonium hexafluorophosphate. The resulting precipitate was filtered, washed with water and ethanol, and then dried at 25°C for - days to obtain diazo resin 2.

Synthesis of Diazo Resin 3 Diazo Resin 3 was synthesized in the same manner as in the synthesis of Diazo Resin 2 using 4.2 g (25 mmol) of P-methoxybenzoic acid instead of p-hydroxybenzoic acid.

The other diazo cocondensation resins mentioned above can also be synthesized by the same method as the diazo resins 1 to 3 above.

Synthesis of Diazo Resin 4 (Comparative Diazo Resin) 14.5 g (50 mmol) of p-diazophenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise to this reaction solution. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours while cooling with water.

This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and 6
．． A cold concentrated aqueous solution of 8 g of zinc chloride was added. The resulting precipitate was filtered and washed with ethanol.
It was dissolved in 0 mj2 of pure water. To this liquid was added a cold concentrated aqueous solution in which 15 g of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried at 30°C for 1 day to obtain diazo resin 4.
I got it.

The photosensitive diazo cocondensation resin described above is preferably used in combination with an alkali-soluble or alkali-swellable lipophilic polymer compound used as a binder resin.

As this lipophilic polymer compound, the following (1) to 02)
Examples of the monomers shown in the following are copolymers whose structural units usually have a molecular weight of 20,000 to 200,000.

(1) Acrylamides, methacrylamides, acrylic esters, and methacrylic esters having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)alkuramide or N-(4-hydroxyphenyl)methacrylamide, 0-1m -1P-, hydroxystyrene, 0-m -1P-hydroxyphenyl acrylate or methacrylate, (2) acrylic esters having aliphatic hydroxyl groups, and methacrylic esters, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic acid hexyl, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate , (substituted) alkyl methacrylates such as N-dimethylaminoethyl acrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, (9) Styrene, α-methylstyrene, methylstyrene, chloro Styrenes such as methylstyrene, QO]
Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, proviny vinyl ketone, and phenyl vinyl ketone, 01) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, Q2) N-vinylpyrrolidone, N-vinylcarbazole, 4 - Vinyl and lysine, acrylonitrile, methacrylate trile, etc. Furthermore, the above monomer may be copolymerized with a monomer that can be copolymerized with the monomer, and the copolymer obtained by copolymerizing the above monomers may be used, for example, with glycidyl methacrylate. , glycidyl acrylate, etc., but are not limited to these.

More specifically, a hydroxyl group-containing copolymer containing the monomers listed in (1) and (2) above is preferred, and an aromatic hydroxyl group-containing copolymer is even more preferred.

The copolymer preferably contains an α,β-unsaturated carboxylic acid listed in (3), and the preferred acid value of the copolymer is from 10 to 100.

The preferred molecular weight of the above copolymer is 40,000 to 150,000.

Furthermore, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolak resin, natural resin, etc. may be added to the above copolymer as necessary.

The photosensitive layer of the present invention can contain a photopolymerizable composition if necessary.

The photopolymerizable composition contains a photopolymerization initiator and an addition polymerizable unsaturated compound, and preferably a binder resin is added. As this binder resin, binder resins used in combination with diazo resin can be used, and more preferably, those disclosed in Japanese Patent Publications No. 49-17874, JP-A No. 59-46643, JP-A No. 57-71048, etc. A photocrosslinkable copolymer having an ethylenically unsaturated bond in the side chain, which is described in Examples include a carboxylic acid half ester polymer obtained by reacting erythritol triacrylate, and a polymer obtained by adding glycidyl methacrylate to a styrene/acrylonitrile/acrylic acid copolymer.

Next, a typical synthesis example of the above-mentioned polymer compound used as a binder resin in the photosensitive layer will be shown as polymer compound 1.
Synthesis of N-(4-hydroxyphenyl)methacrylamide 35
g1 Acrylonitrile 10g, ethyl acrylate 2.
0 g, 15 g of methyl methacrylate, and 1.85 g of abbisisobutyronitrile were dissolved in 180 ml of ethanol, and the mixture was purged with nitrogen and then heated at 70 to 80°C for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 60 g of lipophilic polymer compound 1.

When the molecular weight of this lipophilic polymer compound 1 was measured by GPC, the weight average molecular weight was 20,000.

Synthesis of polymer compound 2 2-hydroxyethyl methacrylate) 50.0 g (
0,385 mol), acrylonitrile 20g (0,37
A mixture of 25 g (0.25 mol) of methyl methacrylate, 5 g (0.058 mol) of methacrylic acid and 1.2 g of benzoyl peroxide was added to 300 g of ethylene glycol monomethyl ether heated to 100°C for 2 hours. dripped. After the dropwise addition was completed, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, the mixture was diluted with methanol and poured into water 51 with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 90 g of lipophilic polymer compound 2.

When the molecular weight of this lipophilic polymer compound was measured by GPC, the weight average molecular weight was 65,000.

Next, examples of the fluororesin constituting the ink repellent layer in the plate material of the present invention include JP-A Nos. 52-74404, 52-74405, 58-83011, and 58-
No. 88750 and No. 5B-90524, etc., which are conventionally known or disclosed in Japanese Patent Application No. 63
It is possible to use any of the fluororesins that have been proposed by the present applicant in applications such as No. 182466, No. 63-237680, and No. 63-288129.

Preferably, Japanese Patent Application Nos. 63-182466 and 63-2
The fluororesins described in the specifications of No. 37680 and No. 63-288129 are used, and for example, the following can be used.

(1) It has the following structural unit in the molecule, and CF's
CF t CF-1CF, -0--cFz-
o--CF-0- (Fluorine content is 30% by weight or more, preferably 50% by weight or more) and the compound in the molecule, directly or through a crosslinking agent, between fluororesins and/or in the photosensitive layer A fluororesin that has functional groups that can react with each other to form bonds.

Examples of the above-mentioned functional groups include the following functional groups.

OH, COOH, NH3, NH- The above fluororesin can be obtained by copolymerization of a fluorine-containing monomer and a monomer having the above functional group.

Specifically, the fluororesins exemplified below are preferably used.

■ Copolymer resin of perfluoroalkyl (meth)acrylate and allyl methacrylate ■ Copolymer resin of perfluoroalkyl (meth)acrylate and (meth)acrylic acid ■ Perfluoropolyether (meth)acrylate and (meth)acrylic acid Glycidyl (
Resin with added meth)acrylate■ Perfluoroalkyl(meth)acrylate and 2-hydroxyethyl(
Copolymer resin of meth)acrylate, alkyl(meth)acrylate, and acrylonitrile■ Perfluoroalkyl(meth)acrylate and 2-
Resin obtained by adding 2-methacroyloxyethyl isocyanate to a product obtained by copolymerizing hydroxyethyl (meth)acrylate, alkyl (meth)acrylate, and acrylonitrile Between the fluororesin layer and the photosensitive layer according to the present invention The bonding between the fluororesin and the photosensitive layer is achieved by dissolving the fluororesin and an optionally added crosslinking agent in an appropriate solvent, applying the solution onto the photosensitive layer, drying it, and then subjecting it to heat treatment. The compound inside is crosslinked via a crosslinking agent or directly,
It is formed.

In the present invention, the fluororesin layer is preferably crosslinked, and the crosslinking agent used together with the fluororesin has two functional groups in its molecule that can react with the functional groups described in item (1) above. Preferably, a polyisocyanate compound such as hexamethylene diisocyanate, toluylene-2,4-diisocyanate, etc. is used in combination with a fluororesin having a hydroxyl group.

Next, silicone rubber, which is another material constituting the ink barrier in the plate material of the present invention, will be explained.

The above-mentioned silicone rubber is a linear organic polyester having a repeating unit represented by the following general 2), having a molecular weight of several thousand to several hundred thousand, and having a hydroxyl group bonded in the main chain or at the end of the main chain. Those containing siloxane as a main component are preferably used.

-Montana■ -+5t-Oh Here, n is an integer of 2 or more, and R is an alkyl group having 1 to 10 oxygen atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, or a silanol group (OH group). The silanol group (OH group) may be present either in the main chain or at the end of the main chain, but is preferably at the end.

The silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.

(1) R-31-(-OR') (2) R-3i-←0Ac) (3) R-3i-←0N-CR'z)tHere, R is -
The position of the polymer represented by formula (a) (synonymous with R, which is a negative group), R' is an alkyl group such as a methyl group or ethyl group, and Ac is an acetyl group.

These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Corporation.

Other useful silicone rubbers are produced by the reaction of the above-mentioned base polymer with a silicone oil having repeating units represented by the following general formula (2), or silicone rubbers in which approximately 3% of R is vinyl groups. It can also be obtained by an addition reaction with a base polymer or a reaction between the above silicone oils.

General 2■ (In the formula, R has the same meaning as R, which is a substituent of the polymer shown in the above-mentioned -Momona■, m is an integer of 2 or more, and n is an integer of 0 or 1 or more.) Like this. In order to obtain silicone rubber by a crosslinking reaction, the crosslinking reaction is carried out in the presence of a catalyst. As this catalyst, organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, manganese, etc., such as dibutyltin laurate, tin(n) octoate, cobalt naphthenate, etc., or chloroauric acid, etc. are used. .

In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed. Silicone rubber mixed with filler in advance is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, RT
(2) Alternatively, LTV silicone rubber disverzidine is preferably used. An example of this is syt Off 23.5RX-257 manufactured by Toray Silicone.
, 5H23T and other silicone rubber dispersions for paper coating.

In the present invention, it is preferable to use condensation and crosslinking type silicone rubber.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve adhesiveness.

Examples of preferable silane cuff pulling agents include the following.

(a) HJCH*CHgNH(CHg) sst
(OCHs) s(b) hNcHzclhNH(C
Hz) zsi (OCHz)! (CHi) (C)
H2N(CII) 5si(OBt)s The silicone rubber layer used in the present invention can further contain a small amount of photosensitizer, and silicone rubber can be used as the material for the ink repellent layer in the plate material of the present invention. is preferred.

The photosensitive layer used in the present invention contains dyes (for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue" for making images visible after exposure or development).
603 (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. agents (e.g. Pluronic L64 (
(manufactured by Asahi Denka Co., Ltd.), plasticizers (e.g., polyethylene glycol, tricresyl phosphate, acrylic acid or methacrylic acid polymers, etc.), stabilizers (e.g., phosphoric acid, oxalic acid, tartaric acid, etc.) to impart flexibility to the coating film. etc.) can be contained.

The fluororesin layer and silicone rubber layer used in the present invention can be formed by dissolving the fluororesin or silicone rubber, respectively, in a suitable solvent, coating the solution on the photosensitive layer, and then drying.

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 a metal plate such as aluminum, zinc, copper, or steel. , as well as chromium, zinc,
Examples include metal plates plated or vapor-deposited with copper, nickel, aluminum, iron, etc., paper, plastic films, glass plates, resin-coated paper, and paper covered with metal foil such as aluminum.

Among these, aluminum plates are particularly preferred.

In order to improve the adhesion between the support and the photosensitive layer, the support may be subjected to various surface roughening treatments, if necessary.

In addition, in order to improve the adhesion between the photosensitive layer and the support,
Before coating the support with the photosensitive layer, a primer layer may be provided on the support, and examples of materials constituting this primer layer include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, and vinyl chloride. Resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin,
Examples include polyacrylonitrile bucdiene and polyvinyl acetate. This primer layer may contain an ultraviolet absorber to prevent halation.

Further, as the anchor agent constituting the primer layer, for example, a silane coupling agent, a silicone primer, 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 1
00 to 300 μm, the photosensitive layer is 0.05 to 10 μm, preferably 0.5 to 5 μm, the ink repellent layer is 0.01 to 10 μm, preferably 001 to 18 m if it is a fluororesin layer, and In the case of a silicone rubber layer, 0.5 to 100 μm, preferably 0.5 to 10 μm
It is.

The plate material of the present invention may have a protective layer on the top surface of the ink repellent layer, if necessary.

The plate material of the present invention that does not require dampening water is 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.

Note that, if necessary, a primer 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 silicone rubber solution or a fluororesin and a crosslinking agent are coated on the photosensitive layer in a similar manner, and heat-treated at a temperature of usually 100 to 120°C for several minutes to sufficiently cure the fluororesin layer or Form a silicone rubber layer. If necessary, a protective film can be provided on the fluororesin layer or silicone rubber layer using a laminator.

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

A positive film, which is an original, is vacuum-adhered to the surface of a positive plate material and exposed. The light sources for this exposure include mercury lamps, carbon arc lamps, xenon lamps, and
Metal halide lamps, fluorescent lamps, etc. are used.

Then, the positive film is peeled off and developed using a developer. As the developer, any known developer for plate materials that do not require dampening water can be used.For example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G")
Manufactured by Esso Chemical Co., Ltd., aliphatic hydrocarbons (trade name of aliphatic hydrocarbons) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (trichloroethylene, etc.) added to the following polar solutions. It is preferable that

Alcohols (methanol, ethanol, etc.), water, 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 simultaneously with development by adding a dye such as crystal violet or astrazone red to the developer.

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

By the above development, the fluororesin or silicone rubber in the unexposed areas is removed and the photosensitive layer, and in some cases the primer layer or the support, is exposed to light, yielding a printing plate with the fluororesin or silicone rubber layer remaining in the exposed areas. .

〔Example〕

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

In the following description, "parts" means "parts by weight" unless otherwise specified.

Example 1 Production of aluminum plate a An aluminum plate with a thickness of 0.2 mm was degreased by immersing it in a 3% aqueous sodium hydroxide solution, washed with water, and then soaked in hydrochloric acid with a concentration of 1%.
and at a temperature of 25°C in an aqueous solution with a boric acid concentration of 1%.
Electrolytic etching was performed for 5 minutes at 3A/dm'',
After washing with water, 1.
Anodize for 2 minutes at 5 A/d m'', wash with water, and add to a 1% sodium metasilicate aqueous solution at a temperature of 85°C.
for 37 seconds, and then soaked in water (pH 8.5) at a temperature of 90"C.
) for 25 seconds, washed with water, and dried to obtain aluminum plate a.

A photosensitive composition having the composition shown below was applied to the aluminum plate a thus produced, and dried at 100°C for 2 minutes to form a photosensitive layer with a thickness of 0.5 μm.

[Photosensitive composition]

Diazo resin 1 40 parts Polymer compound 1 60 parts Victoria Pure Blue BOH 1 part (manufactured by Odugaya Kagaku Co., Ltd., dye) Methyl cellosolve 900 parts Then,
The following silicone rubber composition was coated on the photosensitive layer at a dry weight of 2.0 g/m'' and dried at 120° C. for 2 minutes to obtain a lithographic printing plate material that did not require dampening water.

[Silicone rubber layer composition]

Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52,000) 100 parts triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar G (
(manufactured by Esso Chemical) 900 copies After a positive film was vacuum-adhered to the upper surface of the above plate material, it was exposed to light using a metal halide lamp as a light source. Next, it was developed using the following developer. During development, by rubbing the surface of the plate material with a development pad, the photosensitive layer and silicone rubber layer in the unexposed areas were removed, and a lithographic printing plate was obtained.

[Developer composition]

30 parts of Isopar H 50 parts of diethylene glycol dimethyl ether 20 parts of tripropylene glycol monomethyl ether 5 parts of diethyl succinate
Attach the above printing plate to a small dot sprint printing machine with the dampening water supply device removed, and use the tag P PRO manufactured by Osaka Ink Manufacturing Co., Ltd.
CII! SS enemy R11! When printed using D H, 20,000 prints with good dot reproducibility were obtained.

Examples 2 to 4 and Comparative Examples Plate materials and materials were used in the same manner as in Example 1, except that diazo resins and polymeric compounds as shown in Table 1 below were used in the photosensitive compositions. Examples 2 to 4 and the comparative example were carried out, respectively, by producing printing plates and then printing as in Example 1 with these printing plates, and the stiffness obtained in that case and the stiffness of Example 1 The results are also shown in Table 1.

In Examples 2 to 4, the number of printed matter with good dot reproducibility was obtained as shown in Table 1, whereas in the comparative example, since the diazo resin was different from that of the present invention, Only 8,000 prints with poor point reproducibility were obtained.

Below is a blank table (effects of the invention) As is clear from the above explanation, according to the present invention,
Provided is a lithographic printing plate material in which the adhesion between a photosensitive layer and an ink repellent layer is improved, thereby forming a printing plate with excellent stiffness resistance and image reproducibility, and which does not require dampening water.

Claims (1)

[Scope of Claims] A lithographic printing plate material that does not require dampening water and is formed by laminating a photosensitive layer and an ink repellent layer on a support in order from the support side, wherein the photosensitive layer is represented by the following general formula I. A lithographic printing plate material that does not require dampening water and is characterized by containing a diazo resin having repeating units as a photosensitive substance. General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents the residue of an aromatic diazonium compound that can be condensed with formaldehyde, provided that A represents two or more residues that are the same or different. represents a group, B is
Represents a residue of an aromatic compound having one or both of at least one carboxyl group and at least one hydroxyl group, provided that X represents a diazo anion, Y represents an intermediate link derived from a condensable carbonyl compound, and m and n each represent 1
Represents an integer between ~200.