JPS5997136A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain satisfactory printed material free from a stain due to printing by adding a specified diazo resin to a photosensitive composition used in the manufacture of a photosensitive lithographic printing plate or the like. CONSTITUTION:To a photosensitive composition contg. a high molecular compound having hydroxyl groups is added >=0.1wt% diazo resin represented by the formula, wherein R1 is alkyl, alkoxy, hydroxyl, carboxy ester or carboxy, R2 is H, 1-3C alkyl or phenyl, R3 is H or 1-3C alkoxy, X<-> is the anion of a compound for making the diazo resin insoluble in water, and (n) is an integer of >=1. The prepd. photosensitive composition shows superior solubility in an org. solvent for coating. The composition is dissolved in the solvent, coated on a support, dried, and imagewise exposed, and the unexposed part is removed by development with an alkaline developer. The composition shows superior developability. The resulting relief image has high wear resistance, sensitivity and adhesive strength to the support, and when it is used as a printing plate, many sheets of satisfactory printed material are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition containing a novel diazo resin compound, and particularly to a photosensitive composition suitably used in a photosensitive lithographic printing plate.

The majority of the photosensitive substances conventionally used in printing materials that have been given photosensitivity in advance (so-called 28 plates) that act on the negative (2) are diazonium compounds, especially those with two diazonium salt skeletons. This is a diazonium salt (so-called diazo resin) having the above-mentioned island molecules connected to each other.

When such a diazo resin is coated on a suitable support such as paper, plastic or metal and exposed to actinic light through a transparent negative, the diazo resin in the exposed areas decomposes and becomes insoluble and lipophilic. Changes to

On the other hand, the surface of the support is exposed by dissolving and removing the unexposed areas with water. If a support having a surface that has been previously subjected to a hydrophilic treatment is used, the hydrophilic layer will be exposed in the unexposed areas by development. Therefore, when performing offset printing, this portion receives water and repels ink.

In addition, the decomposed portion of the diazo resin exhibits lipophilic properties, repelling water and accepting ink. Such printing materials thus give so-called negative-positive printing plates.

Conventionally, the method for linking diazonium salt skeletons in such diazo resins is to combine an aromatic diazonium compound and a reactive carbonyl-containing organic condensing agent, particularly aldehydes or acetals such as formaldehyde and acetaldehyde, in an acidic medium. A combination method was used.

The most typical example is a formaldehyde composite of p-diazodiphenylamine. A method for producing a diazo resin using the coupling method is described, for example, in U.S. Patent No. 2t7911Fg'
No. 30!0102, No. 33//lOj, and No. 327707≠ Meiri 1.

In the diazo resin linked by the reactive carbonyl, when the counter anion of the diazonium salt is an inorganic anion such as a mineral acid such as hydrochloric acid, hydrochloric acid, acid and phosphoric acid, or a double salt with zinc chloride, water Personality: Unstable against moisture,
There is a problem that storage stability deteriorates. Historically, in order to improve storage stability, water-soluble diazo resin was reacted with an organic coupling agent such as a phenolic hydroxyl group-containing aromatic compound, an acidic aromatic compound, or an acidic aliphatic compound to form water-insoluble 1-111i1. The method to use is Tokuko Akihiro 7-/
No. 67 and US Pat. No. 330,030. However, this type of diazo resin does not have sufficient solubility in organic coating solvents such as alcohols, ketones, and glycol ethers.

Furthermore, in order to make the diazo resin water-insoluble and soluble in organic solvents, diazo resins containing halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid, and perhalogenated acids such as persulfuric acid and periodic acid as counteranions are used. Tokukaisho about the use of resin! ≠-9rl, Publication No. 13, same j A-
It is described in the specification of Publication No. /2/03/. However, these diazo resins have extremely poor solubility in alkaline developing solutions, and during development, the diazo resin in unexposed areas remains on the support without being developed. Since such diazo resins are water-insoluble and lipophilic, they tend to accept ink during printing, causing printing stains and making it difficult to obtain good printed materials.

An object of the present invention is to provide a photosensitive composition containing a novel diazo resin compound in which the koji point has been solved. That is, the object of the present invention is to provide a photosensitive composition containing a diazo resin compound, which has improved solubility in an organic solvent and also has improved developability when developing a non-image area with alkali after image exposure.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that in a photosensitive composition containing a diazo resin and a polymer compound having a hydroxyl group, the diazo resin represented by the following general formula (1) is added to the photosensitive composition. It has been found that the object of the present invention can be achieved by a photosensitive composition characterized in that the photosensitive composition contains at least 007% by weight of -l-.

General formula (2) In the formula, R1 is an optionally substituted alkyl, alkoxy, hydroxy, carboxy ester, carboxy group, preferably an alkyl, alkoxy, or hydroxy group, preferably alkyl having a carbon number of /~, Indicates an alkoxy or hydroxy group having 1 to 3 carbon atoms. R2 is a hydrogen atom, an alkyl group having up to 3 carbon atoms, a phenyl group, preferably a hydrogen atom,
Methyl 7- group, historically preferably represents a hydrogen atom.几3 is a hydrogen atom,
It represents an alkoxy group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methoxy group. n is an integer of 7 or more, preferably n is /
- This is the case when the ratio of the evening meal is more than Omorch.

X- represents an anion of a compound that makes the diazo resin insoluble in water.

Specifically, compounds having a phenolic hydroxyl group such as phenol, aliphatic carboxylic acids and their salts such as fluorocapric acid, isopropylnaphthalenesulfonic acid, ≠, μ′-biphenyldisulfonic acid,! -Nitroorthotoluenesulfo 7m% -5'-sulfosalicyl fL 2 + j-') Methylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfone H13--i romobenzenesulfonic acid, λ-chlorotarnitrobenzenesulfonic acid, 2-fluorocafrylnaphthalenesulfonic acid, l-s7toltersulfonic acid, λ-methoxy≠-hydro Oxy! - Aromatic sulfonic acids and their salts such as pensoyl-benzenesulfonic acid and para-toluenesulfonic acid, halogenated Lewis acids and their salts such as tetrafluoroboric acid and hexafluorophosphoric acid, and perchloric acid and periodic acid. These include perhalogen acids and their salts.

Particularly preferred among these are λ-methoxyguhydroxybenzoylbenzenesulfonic acid, tetrafluoroboric acid, and hexafluorophosphoric acid.

The diazo resin used in the present invention (hereinafter referred to as the diazo resin of the present invention) is, for example, μ′-hydroxy≠
-diazodiphenylamine, μ'-alkyl-diazodiphenylamine (such alkyl groups include, for example, methyl, ethyl, propyl, butyl, amyl groups, etc.)
, Hiro'-alkoxy l-diazodiphenylamine (such alkoxy groups include methoxy, ethoxy, propoxy groups, etc.) and a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, etc. in molar ratios. Each /:/~/:0. jt
, preferably i:o, r to/:0゜6 in an acidic medium, and a reaction product of an ina compound obtained by condensing the diazo resin of the present invention with the above-mentioned compound that makes the diazo resin of the present invention insolubilized in water. be.

Specific examples of the above-mentioned diazo monomers include ≠′-hydroxy-Hiro-diazodiphenylamine, ≠′-methoxy≠-diazodiphenylamine, μ′-ethoxy-Hiro-
Diazodiphenylamine, Hiro'-n-propoxy≠-
Diazodiphenylamine, ≠′-Propoxy-Hiroshi-
Diazodiphenylamine, ≠'-methyl-≠-diazodiphenylamine, Hiro'-ethyl≠-diazodiphenylamine, 41-n-propyl-gudiazodiphenylamine, Hiro/t-propyl-gudiazodiphenylamine, l -n-butyl-gudiazodiphenylamine , ≠'-Hydroxymethyl-≠-diazodiphenylamine, ≠'-β-hydroxyethyl-Hiro-dibudiazodiphenylamine, r-hydroxypropyl-gudiazodiphenylamine, ≠'-methoxymethyl-≠-
Diazodiphenylartamine, ≠'-ethoxymethyl-≠-diazodiphenylamine, Hiro'-β-methoxyethyl-Hiro-diasocyphenylamine, ≠'-β-ethoxyethyl≠-diazodiphenylamine, San'-carboxy t- Diazodiphenylamine, v'-carbomethoxy-gudiazodiphenylamine, j'-carboethoxy-μm diazodiphenylamine, etc., and their λ'- or 3'-positional isomers are included.

These diazo monomers also include those in which an alkoxy group having up to 3 carbon atoms is substituted at the 3-position.

The content of the diazo resin of the present invention contained in the photosensitive composition is /-10% by weight, preferably 3 to 20% by weight. Furthermore, in addition to the diazo resin of the present invention, JP-A Showa o-1ir
Diazo compounds such as those described in the specifications of RO2 and Japanese Patent Publication SHOTA 2-7JAv may be used in combination.

In the present invention, examples of the polymer compound containing a hydroxyl group used include a copolymer of a monomer represented by the following general formula (■) and another monomer.

1 CH2; C C00(CH2CHO-)nH 几2 (II) In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, methyl, ethyl, or chloromethyl group, and n is an integer of /-10 shows.

Examples of other monomers in the copolymer include acrylonitrile, methacrylatetrile, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers,
These include vinyl esters, styrenes, crotonic acid esters, etc., and are selected from compounds having one or more addition-polymerizable unsaturated bonds. Specifically, for example, acrylic esters 1 such as alkyl acrylates (e.g. methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic & f-t-octyl) , chloroethyl acrylate, 2-nodimethylhydroxypropyl acrylate, terhydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate) Niaryl acrylate (e.g. phenyl acrylate): Methacrylic acid esters, e.g. alkyl methacrylate (e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate,
amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, ≠-hydroxybutyl methacrylate,! -Hydroxypentyl methacrylate, λ・2-dimethyl-3-
hydroxy-7propyl methacrylate, trimethylolpropane monoacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl acrylate, etc.), aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamides , for example, acrylamide, N-alkylacrylamide, (the alkyl group includes, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, hensyl group) ), N-arylacrylamide (such aryl groups include, for example, phenyl, tolyl, nitrophenyl, naphthyl, and hydroxyphenyl groups).

), N-N-dialkyl acrylamide (the alkyl group includes a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.).

), N-l 3-N-diarylacrylamide (the aryl group includes, for example, a phenyl group), N-methyl-N-
Phenyl acrylamide, N-hydroxyethyl-
Methylacrylamide, henoacetamidoethyl
N-acetylacrylamide, etc.: Methacrylamides, such as methacrylamide, N-alkyl methacrylamide (the alkyl group includes methyl group, ethyl group, 1
-butyl group, ethylhexyl group, hydroxyethyl group,
Examples include cyclohexyl group. ), N-arylmethacrylamide (the aryl group includes a phenyl group, etc.), N-N-dialkylmethacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N・N-diarylmethacrylamide (
Examples of the aryl group include a phenyl group. ), N
-Hydroxyethyl-N-methyl methacrylamide, N
-Mefk-N-phenylmethacrylamide, N-ethylhephenylmethacrylamide, etc.; Allyl compound 5
For example, allyl esters (eg, allyl acetate, allyl caffronate, allyl caprylate.

Allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, acetone allyl acetate, allyl lactate, etc.), allyloxyethanol, etc. Vinyl ethers, such as alkyl vinyl ethers (e.g. evahexyl vinyl ether, octyl vinyl ether, tethyl vinyl ether, ethylpequin vinyl ether) , phthoxyethyl vinyl ether, ethoxy 7-ethyl vinyl ether, chloroethyl vinyl ether, /-)Ifsil-・λ
-dimethylpropyl vinyl ether, coethyl phthyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether,
butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.)
, vinyl aryl ether such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl λ≠-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthrani ether); vinyl esters, such as vinyl butyrate, Vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl cycloacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.; styrene m, e.g., tif styrene, alkylstyrene (e.g. methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, methylstyrene, hexylstyrene, cyclohexylstyrene, tethylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxy Styrene (e.g. methoxystyrene, ≠-methoxy 3-methylstyrene, dimethoxystyrene), halogenostyrene (
Examples: evachlorstyrene, dichlorostyrene, trichlorstyrene, nato-2chlorstyrene, pentachlorstyrene, bromstyrene, sifuromstyrene.

iodostyrene, fluorostyrene, trifluorostyrene, J--from-≠-trifluoromethylstyrene, fluoro-3-trifluoromethylstyrene, etc.): crotonate esters, such as alkyl crotonate ( For example, ethyl crotonate,
hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (e.g. dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.):
Dialkyls of maleic acid or fumaric acid (for example, dimethyl maleate, dibutyl 7 maleate, etc.) are included. Other generally addition-polymerizable unsaturated compounds that can be copolymerized with the compound represented by the general formula (n) above.
7- Good to have. The general formula (It
The composition ratio of the units represented by ) is preferably 1 molar or more. Also included are homopolymers of monomers represented by the general formula (it), and resins obtained by partially esterifying or etherifying heptaenolic hydroxyl groups, such as phenol novolac resins. In this case, the content of structural units having phenolic hydroxyl groups is /~tO mol, preferably t
~60 molti.

In addition to the above-mentioned polymer compounds, polyvinyl acetal resins such as polyvinyl butyral and polyvinyl formal, shellac, or JP-A Shoj≠-ta It, /≠
A polymer containing a monomer having an aromatic hydroxyl group in its polymer structure as described in the specification of the above publication can also be used as the polymer compound having a hydroxyl group of the present invention.

These hydroxyl group-containing polymer compounds may be used singly or in combination. Contained in the photosensitive composition,
The content of the polymer compound having hydroxyl groups is approximately! O~ Tata! % by weight, preferably about 55% to 5% by weight.

The photosensitive composition of the present invention may contain dyes, pigments,
Performance can also be improved by adding stabilizers, fillers, etc. Good luck dyes include oil-soluble dyes such as C
,1,2t101 (oil red R,R),C,1,,
z/, zoO (oil bluelet @301), C, I
, 7u310 (oil blue), C, 1, evening 20
/j (methylene blue), C, 1, ≠, z r r z
(RiIJ Stalviolet), etc.

The photosensitive composition of the present invention is used by dissolving it in a ml solvent, coating it on a suitable support, and drying it.

The amount applied is approximately 0.00% by dry weight. /-197 m2, preferably 0.3-3 f/m2.

Such solvents include, for example, methanol, ethanol,
Improper tool, n-butanol, t-butanol,
Comethoxyethanol, 2-ethoxyethanol, λ
-methoxyethyl acetate, ethylene glycol, tetrahydrofuran dioxane, dimethyl sulfoxide,
N,N-dimethylformamide, acetone, methyl ethyl ketone, etc. and mixtures thereof are used.

Further, examples of the support on which the photosensitive composition of the present invention is applied include paper, plastics (such as polyethylene,
Paper laminated with polypropylene, polystyrene, etc., such as aluminum (including aluminum alloys).

), zinc, paulownia, etc., such as cellulose diacetate, cellulose triacetate, cellulose fropionate,
Films of plastics such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl azetal, etc.; plastic films laminated with the above metals or paper with steamed M8, etc. is impregnated. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Also preferred is a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. Sho≠r-/1327.

In addition, in the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable that Also, U.S. Patent No. 2,7/41,066 Specification 1! As described in ', an aluminum plate treated by immersion in a sodium silicate aqueous solution after graining, Tokuko Sho ≠ 7-j/2! As described in the above publication, an aluminum plate which is anodized and then immersed in an aqueous solution of alkali gold N-silicate is also successfully used.

The above-mentioned anodizing treatment can be carried out using, for example, an aqueous or non-aqueous solution of inorganic acids such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., or organic acids such as oxalic acid, sulfamino acid, or their salts alone or in combination of two or more. It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution.

It is also preferable to carry out a sealing treatment after graining and anodizing. Such sealing treatment includes silicate natoco/-lium aqueous solution, immersion in hot water and hot water melting containing inorganic or organic salts, and water vapor. This is done by taking a bath, etc.

Also, U.S. Patent No. J, Aj+! ', &A2, silicate electrodeposition is also effective.

The photosensitive composition of the present invention spread on a support has a line 11!
ll image, light is blocked through the transparent original painting with halftone image temple,
The original image is then developed with an aqueous developer to give a negative relief image.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

The photosensitive composition of the present invention has excellent solubility in organic solvents when spread on a support, and also has excellent solubility in organic solvents when applied, dried, and imagewise exposed. Excellent developability. The obtained relief image has good abrasion resistance, oil sensitivity, and adhesion to a support, and when used as a printing plate, a large number of good prints can be obtained.

-22- Next, examples of the present invention will be described, but the mode of carrying out the present invention is not limited thereto.

Example 1゜Thickness 0, Jffffl+ 2S material aluminum plate'
70% of pope sodium phosphate kept at jr100c
After degreasing and graining by immersion in an aqueous solution for 3 minutes, t.

Etching was performed with sodium aluminate at 0C for about 10 seconds. The aluminum plate was then desmutted with a 3% aqueous solution of sodium hydrogen oxide and anodized in 20'F6 sulfuric acid. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 700C for 1 minute. After washing with water and drying, the following photosensitive solution was applied to the obtained aluminum plate using a wheeler and dried for λ minutes at to''c.The dry weight was 2.09 /
It was ~2.

(Photosensitive solution) The photosensitive lithographic printing original plate thus obtained was image-attenuated for 1 minute from a distance of 7 m using d± Photo Film-8 PS light, and then immersed in the following developer for 7 minutes at room temperature. The surface was lightly rubbed with absorbent cotton to remove the unlighted areas to obtain a plain printing plate (1) with a bright blue image.

(Developer) This printing plate (1) was printed on high-quality paper using a GTO printing machine manufactured by Heidel Lug Co., Ltd. using commercially available ink, and about 100,000 good prints were obtained.

Example 2. ~4゜Example 1. Using a wheeler, the following photosensitive solution was applied to an aluminum plate which had been treated in the same manner as above, and then dried at 100C for 2 minutes. After that, Example 1. Exposure in the same manner as
Development was performed to obtain printing plates (If) to (IV).

(Photosensitive liquid) 25- Diazo resin A: ≠′-methoxy μm Hexafluorophosphate of condensate of diazophenylamine and formaldehyde Diaso side resin B: ≠′-hydroxy-t-diazodiphenylamine and condensation of formaldehyde Hexafluorophosphate diazo resin C: ≠ / Hexafluorophosphate printing plates (II) to (IV), a condensate of n-propyl-diazodiphenylamine and formaldehyde, all have good prints of approx. I gave you ioo and ooo pieces.

In addition, to clarify the excellent developability of the diazo resins A, B, and C in alkaline developers, diazo resin D (hexafluorophosphate of a condensate of 4-diazodiphenylamine and formaldehyde) is used.
Example 1. When the solubility in the developer shown in Table 1 was measured, the results were as shown in Table 1.

Table l *l) Temperature λ! ″Value in C Patent applicant: Fuji Photo Film Co., Ltd. 27-

Claims (1)

[Scope of Claims] In a photosensitive composition containing a diazo resin and a polymer compound having a hydroxyl group, a diazo resin represented by the following general formula (I) is added to at least o, i, A photosensitive composition comprising the above. (1) [In the formula, R1 represents an optionally substituted alkyl, alkoxy, hydroxy, carboxy ester or carboxy group, R2 represents a hydrogen atom, an alkyl having 1 to 3 carbon atoms, or a phenyl group, and R3 represents It represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms. Further, X- represents an anion of a compound that makes the diazo resin insoluble in water, and n represents an integer of 1 or more. ]