JPH0229650A - photosensitive composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition, and particularly to a photosensitive lithographic printing plate.

[Background of the invention]

Photosensitive printing plates are generally produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, polymerizing or crosslinking the irradiated areas, and turning the composition into a developer. The areas that are not irradiated with light are eluted into a developer, and each area is divided into an image area that repels water and receives oil-based ink, and a non-image area that repels water and receives oil-based ink. As the photosensitive composition in this case, diazo resins such as a condensate of p-diazodiphenylamine and formaldehyde have been widely used.

However, conventionally known diazo resins have low photosensitivity and
In addition, since it generally does not have alkali solubility, when a photosensitive composition containing it is developed with an alkaline developer after exposure, the developability, especially under under conditions, is poor. Furthermore, there is the problem that a so-called diazo residue is formed in which the diazo resin remains in the form of a film on the surface of the support after development, resulting in a decrease in printability.

In addition, in lithographic printing plates, images are generally formed using the photomechanical method, but in this case, the image lines on the printing plate are reproduced thicker than the image lines of the film original (hereinafter abbreviated as ``dot size''). .

). As a result, in the final printed matter, the shadow halftone dots are distorted, resulting in a printed matter that is significantly different from the original, which is inconvenient.

Therefore, the main object of the present invention is to provide a novel photosensitive composition that has high sensitivity, excellent developability, and small dot size.

(Means for Solving the Problem) The above object is achieved by the photosensitive composition containing a co-condensed diazo resin containing an aromatic compound having at least/one carboxylic acid group and an aromatic diazo compound as constituent units. achieved.

(Specific structure of the invention) The present invention will be explained in more detail below.

The aromatic compound having at least one carboxylic acid group according to the present invention contains an aromatic ring substituted with at least one carboxylic acid group, such as a benzene ring or a naphthalene ring, in the molecule, In this case, the carboxylic acid group may be bonded directly to the aromatic ring or may be bonded via a linking group. Examples of the linking group include alkylene groups having a carbon number/number of carbon atoms.

Moreover, the above aromatic ring may be substituted with a substituent other than a carboxylic acid group. Examples include alkyl groups, alkoxy groups, cyano groups, and halogen atoms having carbon atoms ranging from 1 to 3.

In the present invention, the number of carboxylic acid groups bonded to the aromatic ring is preferably co.

In order for the aromatic compound to be condensed with aldehydes or ketones, it must have at least two unsubstituted sites on the aromatic ring of seven or more aryl groups substituted with at least one carboxylic acid group. is necessary.

Specific examples of aromatic compounds having a carboxylic acid group in the molecule utilized in the present invention include p-methylbenzoic acid, p-
etquin benzoic acid, o-m-p-methylbenzoic acid,
0-1m-p-chlorobenzoic acid, O-5'm-p-
cyanobenzoic acid, 3. Hiro-dimethoxybenzoic acid, Yu, Kuu-dimethoxybenzoic acid, Co, Hiro-dimethylbenzoic acid, gauge methylaminobenzoic acid, guanilinobenzoic acid, phenoxyacetic acid, q-methquinphenylacetic acid, p-phenoxybenzoic acid, N-phenyl glycine, isophthalic acid,
Terephthalic acid, DL-mandelic acid, acetylsalicylic acid, cinnamic acid, /-naphthalenecarboxylic acid, conaphthalenecarboxylic acid, 2,3-naphthalenedicarboxylic acid.

All examples include 6-naphthalene dicarboxylic acid, among which p-methoxybenzoic acid, p-methoxybenzoic acid,
p-ethoxybenzoic acid, o-m-, p-methylbenzoic acid, o-, m-, p-chlorobenzoic acid, 2. '1. -dimethoxybenzoic acid, q-dimethylaminobenzoic acid, q-
These include anilinobenzoic acid, p-7 enoxybenzoic acid, N-phenylanthranilic acid, terephthalic acid, cinnamic acid, l-naphthalenecarboxylic acid, and the like.

The aromatic diazo compound used in the present invention is not particularly limited as long as it has a diazonium group directly bonded to the aromatic ring. Diphenylamine tetrafluoroboric acid J f-diazodiphenylamine hexafluoride phosphate, q-morpholino-benzenediazonium tetrafluoroborate, a-(N-ethyl-N-hydroxyethyl)-aminobenzenediazonium sulfate, F-
N,N'-dimethylaminobenzenediazonium hexafluorophosphate, and g-hydroxy-2-naphthalenediazonium tetrafluoroborate. Among these, particularly preferred aromatic diazo compounds include cudiazodiphenylamine salts.

The photosensitive diazo cocondensation resin according to the present invention can be prepared by a known method,
For example, Photographic Science and Engineering (Photo.

Sci-+ Enge) Volume 1, Page 33 (7
97,7), U.S. Pat. Aromatic compounds and aldehydes, such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone and acetophenone, are polycondensed, aromatic diazo compounds, and aldehydes or ketones may be freely combined with each other. Furthermore, it is also possible to mix and co-condense one or more of each. At that time, the charging molar ratio of the aromatic compound having a carboxylic acid group and the aromatic diazo compound was 0:0. /~o, /: t; preferably l:0.5
~O0,2:l, preferably /:/~0.2:
/ is. ! In the case of an octopus, the molar ratio of the total of the compound having a carboxylic acid group and the aromatic diazo compound to the aldehyde or ketone is usually i:o, t, ~l:=, preferably t:o, li~l:t , S and reacted at a low temperature for a short time, for example, about 3 hours, to obtain a cydiazo resin. The counter anion of the diazo resin used in the present invention is:
It contains an anion that forms a stable salt with the diazo resin and makes the resin soluble in organic solvents. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids, with typical examples being methane sulfonic acid, chloroemene sulfonic acid, dodecane sulfonic acid, and benzene sulfonic acid. acids, toluenesulfonic acid, menthylenesulfonic acid, and anthraquinonesulfonic acid, cohydroquine-V-methoxybenzophenone-5-sulfonic acid: l,2','I,'I'-tetrahydroxybenzophenone, /, 2. ,? −)
Lyhydroxybenzophenone! ,,2',ti
-) Hydroxyl group-containing aromatic compounds such as hydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, perhalogen acids such as ClO2, IO, etc., but are not limited to these. It's not a thing.

Among these, particularly preferred are hexafluorophosphoric acid, tetrafluoroboric acid, and cohydroxy-gumethoxybenzophenone-5-sulfonic acid.

Specific examples of the diazo cocondensation resin in the present invention include p
- Methoxybenzoic acid - Gudiazodiphenylamine - Formaldehyde resin - Hexafluorophosphate, p-ethoxybenzoic acid - q-Diazodiphenylamine - Formaldehyde resin - Hexafluorophosphate, O-, m-r monomethylbenzoic acid - &-Diazodiphenylamine-formaldehyde resin-hexafluorophosphate, OHrrl *p-chlorobenzoic acid-goudiazodiphenylamine-formaldehyde resin-hexafluorophosphate,! 4-dimethoxybenzoic acid-q-diazodiphenylamine-formaldehyde resin-hexafluorophosphate l-dimethylaminobenzoic acid-diazodiphenylamine-formaly) resin-hexafluorophosphate, terephthalic acid-gadiazodiphenylamine - Formaldehyde resin - hexafluorophosphate, cinnamic acid - q-diazodiphenylamine - formaldehyde resin - hexafluorophosphate, Oyl'n + p-cyanobenzoic acid - gudiazodiphenylamine - formaldehyde resin - tetrafluoride Borate, co, lI dimethylbenzoic acid-V-diazodiphenylamine-formaldehyde resin-tetrafluorobalate, guanilinobenzoic acid-
Gudiazodiphenylamine-formaldehyde resin-
Tetrafluorobalate, p-7 enoxybenzoic acid-q-diazodiphenylamine-formaldehyde resin-tetrafluorobalate, N-phenylglycine-Hiro-diasocyphenylamine-formaldehyde resin-tetrafluoride Inphthalic acid salt - Hiroshi - Diazodiphenylamine - Formaldehyde resin - Tetrafluorobaltate, Acetylsalicylic acid - φ- Diazodiphenylamine - Formaldehyde resin - Tetrafluorobalate salt, - Mononaphthalenecarboxylic acid - Gu Diazodiphenylamine-formaldehyde resin-tetrafluoroborate, co,3-naphthalenedicarbone e-<
z-diazodiphenylamine-formaldehyde resin-
Tetrafluorobalate, 6-naphthalene dicarboxylic acid
9-Diazodiphenylamine-formaldehyde resin-
Tetrafluorobalate, Coumethoxyphenylacetic acid - Gudiazodiphenylamine - Formaldehyde resin - Cohydroxy-Hiroshi - Methoxybenzophenone-5-sulfonate, p-7 enoxyacetic acid - Gudiazodiphenylamine - Formaldehyde resin - Cohydroxy methoxypenzophenone-5-sulfonate, etc., particularly preferably p-methoxybenzoic acid-9-diazodiphenylamine-formaldehyde resin-hexafluorophosphate, p-ethoxybenzoic acid-ridiazo Diphenylamine-formaldehyde resin-hexafluorophosphate, Orrn
+p-Chlorbenzoic acid-q-diazodiphenylamine-
Formaldehyde resin - hexafluorophosphate, co, tI-dimethoxybenzoic acid gudiazodiphenylamine - formaldehyde resin - hexafluorophosphate, p-methylbenzoic acid - diazodiph, enylamine-formaldehyde resin - hexafluorophosphate, co , terdimethylbenzoic acid-9-
Diazodiphenylamine-formaldehyde resin-tetrafluorobalt salt, Guanimariobenzoic acid-l-diazodiphenylamine-formaldehyde resin-tetrafluorobaltate, N-phenylglycine-Goudiazodiphenylamine-formaldehyde resin-47 Oxyborate, cornaphthalene dicarphonic acid
Gu-diazodiphenylamine-formaldehyde resin-
Tetrafufluoride is a salt of salt.

The diazo cocondensation resin of the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions, but it is effective for the purpose of the present invention. In order to serve, the molecular weight should be about tIoo to /0
．． 000 g can be used, but preferably about
oo to s and ooo are suitable.

The photosensitive diazo resin used in the present invention usually contains 3 to 60% by weight, preferably 3 to 3% by weight, in the solid content of the photosensitive composition.
0 weight ratio is included.

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

As this lipophilic polymer compound, the following (1) to (b) are used.
Examples include copolymers whose structural units are monomers shown in the following, and which usually have a molecular weight of λ to 200,000.

(1) Acrylamides, methacrylamides, acrylic esters, and methacrylic esters having an aromatic hydroxyl group, such as N-(ri-hydroxyphenyl)
Acrylamide or ha N-(tI-hydroxyphenyl)
(2) Acrylic esters having aliphatic hydroxyl groups and methacrylic esters, e.g. Hydroxyethyl acrylate or co-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 , acrylic acid amyl ρ
, hexyl acrylate, octyl acrylate, cochloroethyl acrylate, glycidyl acrylate, N-
(Substituted) alkyl acrylates such as dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
(Substituted) alkyl methacrylates such as amyl methacrylate, cyclohexyl methacrylate, dihydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-
Ethylacrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl, -
Acrylamides or methacrylamides such as N-phenylacrylamide, (7) Vinyl ethers such as ethyl vinyl ether, -monochloroethyl vinyl ether, hydroxyethyl vinyl ether, flobyl vinyl ether, phthyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) Vinyl Vinyl esters such as acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, (9) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, a0 methyl vinyl ketone, ethyl vinyl ketone, propyl Vinyl ketones such as vinyl ketone and phenyl vinyl ketone, olefins such as alpha ethylene, propylene, isobutylene, butadiene, isoprene, (6) N-vinylpyrrolidone, N-vinylcarbazole, govinylpyridine, acrylonitrile, methacrylateril, etc. Furthermore, a heptamer which can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, a copolymer having a hydroxyl group containing the monomers listed in (1) and (23) above is preferred, and a copolymer having an aromatic hydroxyl group is even more preferred.

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

The preferred molecular weight of the above copolymer is 10,000 to 10,000.

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

The lipophilic polymer compound used in the present invention is usually 1IO to 99% by weight, preferably 50% by weight, in the solid content of the photosensitive composition.
Contain up to 93% by weight.

A dye can further be used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, one that changes color tone by reacting with free radicals or acids can be preferably used. Here, "the color tone changes" includes both a change from colorless to a colored tone, and a change from a color to colorless or a different colored tone. Preferred dyes are those that change color tone by forming salts with acids.

For example, Victoria Vinia Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Bruna 603 [manufactured by Orient Chemical Industry Co., Ltd.], Patent Pure Blue [manufactured by Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, methyl green,
Triphenylmethane type, diphenylmethane type, oxidine type, xanthine type, iminonaphthoquinone type, azomethine type, represented by erythrosin B, pesic fuchsin, malachite green, oil red, m-cresol paano p-diethylaminophenyl ace) 7nilide, etc. An example of a color change agent that changes color from a colored or anthraquinone type pigment to colorless or a different colored tone.

It is mentioned as. .

, diphenylamine J □-chloroaniline, /, 2
．． 3-) Riphenylguanidine, naphthylamine, diaminodiphenylmethane, p,p'-bis-dimethylaminodiphenylamine, 8-1 dianilinoethylene, p,
p',p#-tris-dimethylaminotriphenylmethane, p,p'-bis-dimethylaminodiphenylmethylimine, p+p'rp''-)riamino-〇-methyltriphenylmethane, p,p'-pisudimethyl aminodiphenyl-anilinonaphthylmethane, p, p
Examples include primary or primary arylamine dyes represented by ',p''-triaminotriphenylmethane.

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, and more preferred are triphenylmethane-based dyes, particularly Victoria Pure Blue BOI.

The above-mentioned dye is usually contained in the photosensitive composition preferably in a weight ratio of about 0.S to about IO, more preferably about 7 to 5% by weight.

Various additives can be further added to the photosensitive composition of the present invention.

For example, alkyl knee f k to improve coating properties
(e.g. Bar 1-Tylcellulose, Methylcellulose), fluorine-based surfactants, nonionic surfactants [e.g., Pluronic LA≠ (manufactured by Asahi Denka Co., Ltd.)
], a plasticizer to impart flexibility and abrasion resistance to the coating film (
For example, butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, diptyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid. (oligomers and polymers), oil-sensitizing agents for improving the oil-sensitivity of image areas (for example,
Half-esterified styrene-maleic anhydride copolymer with alcohol described in Publication No. S-527), stabilizers [e.g., phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalene, etc.) Sulfonic acid,
q-methoxy: l-hi)” Waxybenzophenone-5
-sulfonic acid, tartaric acid, etc.)]. The amount of these additives added varies depending on the purpose for which they are used, but
Generally, it is o, oi to 30% by weight based on the total solid content.

Such a photosensitive composition is coated on a support. Examples of the support include metal plates such as aluminum plates or alloy plates thereof, zinc plates, copper plates, and stainless steel plates, and plastics such as polyethylene terephthalate and polypropylene.

When the photosensitive composition of the present invention is applied to the production of a photosensitive lithographic printing plate, a support such as an aluminum or alloy plate thereof is provided and used. As a support,
Paper, plastics (e.g. polyethylene, polypropylene, polystyrene, etc.), laminated paper, plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate. , plastic films such as polyethylene, polypropylene, polycarbonate polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with metals such as those mentioned above, steel plates plated with aluminum or chrome, etc. Among these, in particular, Aluminum and aluminum-coated composite supports are preferred.

Further, the surface of the aluminum material is preferably roughened for the purpose of increasing water retention and improving adhesion with the photosensitive layer.

Examples of the surface roughening method include generally known methods such as brush polishing, ball polishing, electrolytic etching, chemical etching, liquid honing, sandblasting, etc., and combinations thereof, preferably brush polishing, electrolytic etching, and chemical etching. Mention may be made of target etching and liquid honing, among which roughening methods involving the use of electrolytic etching are particularly preferred. The electrolytic bath used in electrolytic etching is an aqueous solution containing all acids, alkalis, or their salts, or an aqueous solution containing an organic solvent. Liquid is preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary.

It is desirable that the aluminum plate thus obtained is subjected to anodizing treatment, and particularly preferred is a method of treatment in a bath containing sulfuric acid or phosphoric acid. Furthermore, if necessary, a pore sealing treatment using an alkali silicate or hot water, and a surface treatment such as immersion in a water-soluble polymer compound or a potassium fluorozirconate aqueous solution can be performed.

In order to provide the above-mentioned photosensitive composition on a support, predetermined amounts of the photosensitive diazo cocondensation resin, lipophilic polymer compound, and optionally various additives are mixed with a suitable solvent (methyl heptaroprop, ethyl celloprop). , methyl seron lupacetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof, etc.) to prepare a coating solution of the photosensitive composition, which is coated on a support and dried. Bye. It is desirable that the concentration of the photosensitive composition at the time of coating is in the range of 7 to 50% by weight.

In this case, the coating amount of the photosensitive composition may be about 0,0 to /01/td.

Conventional methods are applied to the photosensitive material coated on the support. That is, by exposing a transparent original image having a line image, a halftone image, etc. to light, and then developing it with an aqueous developer, a negative relief image can be obtained with respect to the original image. Examples of active light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The developer used for developing the photosensitive composition according to the present invention contains a specific organic solvent, an alkaline agent, and water as necessary components. The specific organic solvent herein refers to the non-exposed area (
An organic solvent that can dissolve or swell the non-image area) and has a solubility in water of 70% by weight or less at room temperature (20°C). Such organic solvents only need to have the characteristics described above, and are not limited to the following, examples of which include lumonobutyl acetate, butyl lactate, Carboxylic acid esters such as butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol momyl, and methyl alcohol. Kind:
Alkyl-substituted aromatic hydrocarbons such as xylene; methylene dichloride, ethylene dichloride, and unahalogenated hydrocarbons such as monochlorobenzene. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developing solution should be approximately 1-20% by weight, particularly preferably 2 to 70% by weight, to obtain preferable results.

On the other hand, alkaline agents contained as essential components in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium dibasic or tertiary phosphate, or Inorganic alkaline agents such as ammonium salts, sodium metasilicate, sodium carbonate, ammonium, etc. (B) Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine,
-Organic amine compounds such as n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediamine, and the like.

The content of these alkaline agents in the developer is usually 0.00
05~g weight ratio, preferably O, S~2 weight ratio.

It is preferable to have it. As such a water bathable sulfite, an alkali or alkaline earth metal salt of sulfite is preferable, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the developer composition is usually 0.0
! -F weight attack, preferably 0. / -/I am in charge of weight.

If such a developer is brought into contact with the photosensitive composition after development exposure or rubbed with the developer, the photosensitive composition layer will be formed after 70 to 60 seconds at approximately room temperature to μθ°C. The photosensitive composition in the non-exposed areas is completely removed without adversely affecting the exposed areas, and a photosensitive lithographic printing plate is obtained. However, the present invention is not limited to these examples.

Synthesis of Diazo Resin-7 p-Ethoxybenzoic acid, o g g (/2.s mmol) and diazodiphenylamine sulfate/0
．． 2.9 (3!r mmol) was tlo,”y under water cooling.
g of concentrated sulfuric acid. 3si (9549 mol) 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 IO'cft. After that, stirring was continued under water cooling. This reaction mixture was poured into 1L of ethanol under water cooling, and the resulting precipitate was filtered.

After washing with ethanol, dissolve in 100-ml pure water and add 60% to this solution.
A cold concentrated aqueous solution of 10 g of ordinary salt chloride was added. The resulting precipitate was filtered, washed with ethanol, and dissolved in 15Q-pure water.

To this liquid was added a cold concentrated aqueous solution in which 6.91 ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed, and dried at 30°C day and night to give Diazo Resin-7.
I got it. When the molecular weight of this was measured by GPC (gel permeation chromatography), the weight average molecular weight was about 2,700.

Synthesis of diazo resin-cop-ethoxybenzoic acid to p-chlorobenzoic acid (rag(
diazo resin-
Diazo resin-2 was obtained in the same manner as in the synthesis of Example 1. When the molecular weight was measured by GPC, the weight average molecular weight was approximately 2000.
Met.

Synthesis of diazo resin-3 p-ethoxybenzoic acid'tp-methylbenzoic acid ha? i
Diazo resin 3 was obtained in the same manner as in the synthesis of diazo resin-7 except that (t 2.s mmol) was used. G
When the molecular weight was measured by PC, the weight average molecular weight was approximately QO.

Synthesis of diazo resin-q p-ethoxybenzoic acid and guanilinobenzoic acid J, A
? g (/s, s mmol) and ammonium hexafluorophosphate to ammonium tetrafluoroborate a
Diazo resin-Hiro was obtained in the same manner as in the synthesis of diazo resin-7 except that , asg was used. As a result of GPC measurement, the weight average molecular weight was approximately 0.000.

Synthesis of diazo resin-5 q-anilinobenzoic acid was converted into N-phenylglycine
Diazo resin-5 was obtained in the same manner as in diazo resin-g, except that the amount was changed to g (/2 mmol). When the molecular weight was measured by GPC, the weight average molecular weight was about 2100.

Diazo resin-6 was obtained in the same manner. When the molecular weight was measured by GPC, the weight average molecular weight was approximately 2 mm.

Synthesis of diazo resin (comparative diazo resin) Diazo resin-7 was obtained in the same manner as in the synthesis of diazo resin-6, except that the amount of paraformaldehyde was changed to 80 sg (3 s mmol). When the molecular weight was measured by GPC, the weight average molecular weight was approximately /A00.

[Synthesis of lipophilic polymer compound l]

N-(tI-hydroxyphenyl)methacrylamide 1
0. OII, acrylonitrile 2311, ethyl acrylate 6θl, methacrylic acid jI and azobisin butyronitrile/, 6929 f acetone-methanol/: dissolved in l mixed solution t/amt and after purging with nitrogen 6
Heated at 0°C for 3 hours.

After the reaction was completed, the reaction solution was stirred and poured into 5 tons of water, and the resulting white precipitate was filtered and dried to obtain qog of the lipophilic polymer compound.
Obtained.

When the molecular weight of this lipophilic polymer compound 1 was measured by GPC, the weight average molecular weight was tr, s, 10,000.

[Synthesis of lipophilic polymer compound]

Sea hydroxyethyl methacrylate tISg, acrylonitrile 10/i, ethyl methacrylate 3!11.
The mixture was added dropwise over 2 hours to a mixture of methacrylic acid 109 and 8-g of benzoyl peroxide @ioo°C heated to ethylene glycol monomethyl ether 30011. After the dropwise addition was completed, 300.9 g of ethylene glycol monomethyl ether and 0.3 g of pencil peroxide were added, and the mixture was allowed to react for 9 hours. After the reaction is complete, dilute with methanol and pour into 5 L of water with stirring.The resulting white precipitate is filtered and dried to remove the lipophilic polymer compound. I got an OI.

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

It was 10,000.

[Sand grain production]

The aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, and then anodized in a flathead hydrochloric acid bath at 25° C. for 2 minutes. Next, silicate with t% meta)IJum water soluble'#"fr ℃5.7
The pores were sealed for seconds, washed with water, and dried to obtain an aluminum plate for planographic printing.

Example/-5, Comparative Examples 1 to 3 A photosensitive solution having the following composition was applied to the aluminum plate for lithographic printing obtained as described above, and the coating weight after drying was 8 liters.
9/rr? It was applied so that

Photosensitive liquid composition Lipophilic polymer compound -/, s, o i diazo resin 'Q,
1. Metal halide lamp. The film was exposed for 30 seconds from a distance of Oan, developed with developer-7 having the following composition, and the sensitivity was examined. Next, in order to examine the diazo residue in the non-image area, half of the non-image area of the printing plate thus obtained was exposed again and compared with the area that was not re-exposed. Furthermore, in order to investigate under-developability, development was carried out using a diluted developer solution prepared by adding an equal volume and one volume of pure water to developer solution 2 and 3 to develop the non-image area. (manufactured by Nippon Tsumugi Pharmaceutical ■) Methylselonlupe Combinations of the ioomt lipophilic polymer compound and diazo resin are shown in Table 1.

The thus obtained photosensitive lithographic printing plate was examined for developability of line areas using a negative transparent original image, a step wedge (optical density 3 days), and a developer.

Composition of developer solution-7 Benzyl alcohol Triethanolamine Sodium sulfite Butyl naphthalene Sulfonic acid Sodium water Similarly, non-straight 0 g l! I g 5y iooo y (Development conditions: Developed for aO seconds at s'CK) Next, in order to check the size of one point, each photosensitive solution was applied to the obtained photosensitive planographic printing plate, and UGR, A- 7, and the dot size of the printing plate was measured using Sakura Area Duck 1000 (manufactured by Konica ■).

These results are summarized in Table-7.

(Effects of the Invention) According to the present invention, photosensitive lithographic printing with excellent under-developability, no diazo residue, and small dot size, that is, excellent tone reproducibility, is achieved as shown in Table 7. The plate obtained is extremely useful industrially.

Procedures Amendment (voluntary) Indication of the case Patent Application No. 18001 of 1988, Title of the invention Person making the amendment to the photosensitive composition Applicant Mitsubishi Kasei Corporation et al./Named agent Patent attorney For quality - Others/Name 4 Agent〒
100 Mitsubishi Kasei Corporation Internal Office, 2-5-2 Marunouchi, Chiyoda-ku, Tokyo, (283) 6976 (1) Lines 18 to 19 from directly above No. 32 of the specification [2]
5℃, 3A/d Ugly 2", [25℃, 100A
/ Correct it as d+i”J.

(2) In the 19th to 20th lines from the top of page 32 of the specification, the phrase "in a 5.30% sulfuric acid bath after washing with water" should be replaced with "in a 5.30% sulfuric acid bath after washing with water".
"In sulfuric acid Rakuchu," he corrected.

(3) In the 1st line from the 33rd purchase of the specification, the statement ``2 minute anodizing treatment'' is corrected to ``30 second anodizing treatment''.

that's all

Claims (1)

[Claims] (1) A photosensitive composition characterized by containing a co-condensed diazo resin containing an aromatic compound having at least one carboxylic acid group and an aromatic diazo compound as constituent units.