JPH01179936A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve the sticking property between an image part and a supporting body, and to prevent the peeling off of the image part from the supporting body even by rubbing the image part at the time of developing by incorporating a polymer having a group contg. carboxyl group capable of generating decarboxylation by exposing, and a diazonium compd. in the title composition. CONSTITUTION:The photosensitive composition is composed of the polymer having the group contg. the carboxyl group capable of generating the decarboxylation by exposing in the presence or absence of a sensitizer, and the diazonium compd. The group contg. the carboxyl group is preferably exemplified by a residual group contg. the skeleton of a following compd., namely, indole-3-acetic acid, phenoxy acetic acid, 2-methyl phenoxy acetic acid, etc. The group contg. the carboxyl group is bound to the main chain of the polymer directly or through a linking group Z. Thus, the sticking property between the supporting body and a photosensitive layer is improved by incorporating the diazonium compd. in the composition, and the peeling off of the exposed part of an image from the supporting body is prevented even if the exposed part is rubbed with a sponge at the time of developing.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel photosensitive composition, in particular, it decarboxylates carboxylic acids in polymers with light, changes their solubility in alkaline developers, and improves coexistence. The present invention relates to a photosensitive composition capable of forming a negative image on an original image, which has improved adhesion between a quadrant of a negative image and a support using a diazonium salt.

[Prior art and its problems]

The applicant has discovered that a polymer containing a carboxyl group that undergoes decarboxylation upon exposure to light in the presence or absence of a sensitizer can form a negative image on an original image by exposing and developing the image through the original image. Japanese Patent Application No. 62 concerning the invention of an image forming layer using a polymer of
- Filed as No. 188453.

However, images obtained in this manner do not necessarily have sufficient adhesion to the support, and there is a problem in that the images peel off when rubbed with a sponge during development.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition in which the adhesion of the image area to the support is improved and the image area does not peel off even when rubbed with a sponge or the like during development.

[Structure of the invention]

In order to achieve the above object, the present inventors conducted various studies, and by chance discovered that the above object could be achieved by coexisting a diazonium compound with the above polymer in a photosensitive composition. It has arrived.

The present invention will be explained in detail below.

Preferred polymers having carboxyl group-containing groups that undergo decarboxylation upon exposure in the presence or absence of a sensitizer (hereinafter referred to as polymers of the present invention) are used as the image forming layer of the present invention. The carboxyl group-containing group is represented by the formula: % formula % (), and this group is connected to the main chain of the polymer (P) with or without the linking group Z.

In the above formula (I), X means sulfur, oxygen, a single bond, C=W or;
C=W, :"N-U is preferable in terms of sensitivity.

W means oxygen and sulfur. U means an aryl group, an alkyl group, or a hydrogen atom which may have a substituent. Y means alkylene, arylene, aralkylene, or divalent heterocycle which may have a substituent. k is 0 or 1, and l is 0 or 1.

Further, when X is sulfur, oxygen, a single bond, or; N-1J, -X -+ CH2→-v-COOH is preferably bonded to an aryl nucleus or an aromatic heterocyclic nucleus in terms of sensitivity. In this case, the aryl nucleus or heterocyclic nucleus may be present in the side chain or may be included in the main chain of the polymer.

Preferred carboxyl group-containing groups include residues containing the skeletons of the following compounds.

Indole-3-acetic acid, phenoxyacetic acid, 2-methylphenoxyacetic acid, 3-methoxyphenoxyacetic acid L2-ditrophenoxyacetic acid, 3-chlorophenoxyacetic acid, 4-methylphenoxyacetic acid, n-butoxyacetic acid, thiophenoxyacetic acid, 3-methoxythiophenoxyacetic acid, 2-chlorothiophenoxyacetic acid, 2-methylthiophenoxyacetic acid, 4
-Nitrothiophenoxyacetic acid, n-butylthioacetic acid, phenylacetic acid L2-nitrophenylacetic acid, 4-trophenylacetic acid, 2,4-dinitrophenylacetic acid, benzoylformic acid, 4-chlorobenzoylformic acid, thiobenzoylformic acid,
Pyruvine L N-phenylglycine, N-(3-chlorophenyl)glycine, N-(2,4-dichlorophenyl)glycine, N-(4-acetylphenyl)glycine,
N-(2-nitrophenyl)glycine, N-(2,4-
dinitrophenyl)glycine, N-(4-cyanophenyl)chrycine, N-(2-bromophenyl)glycine,
N-(2-methylphenyl)chrycine, N-(2-methoxyphenyl)glycine, N-(2,4-dimethoxyphenyl)glycine, N-(n-butyl)glycine, N-
Methyl-N-(2-methylphenyl)glycine, N-methyl-N-(4-chlorophenyl)glycine, N-methyl-N-(2-nitrophenyl)glycine, N-methyl-N-(2- methoxyphenyl)glycine, N-<4-
carbamoylphenyl)glycine, N-(4-sulfamoylphenyl)glycine, etc.

These carboxyl group-containing groups are bonded to the polymer main chain with or without the linking group Z. Linking groups include ether bond, amide bond, ester bond,
A urethane bond, a ureido bond, or a linking group containing them. Note that a part of the carboxyl group-containing group may be included in the polymer main chain.

The linking group containing an ether bond, amide bond, ester bond, urethane bond, or ureido bond is represented by the following formula (I
II), (1'V), (V), and (VI).

-L-+-R-L+7R-(III) -L-+-R-L→7 (I”/)-R+L
-R+-L-(V) -R--H-L -R→r (Vl) Here, R represents alkylene, arylene, aralkylene, or a divalent heterocycle, each of which may be different, and L
represent an ether bond, amide bond, ester bond, urethane bond, or ureido bond, which may be different from each other.

n is Oll or 2.

Examples of polymers having groups containing carboxyl groups include acrylic resins, vinyl polymer resins including vinyl alcohol resins, polyurethane resins, polyurea resins, polyvinyl acecool resins, polyamide resins, and epoxy resins. Including, but not limited to:

For example, acrylic resins include homopolymers of monomers represented by the general formula (■) or copolymers with other monomers (eg, acrylic esters, methacrylic esters, etc.).

H2 Furthermore, for example, a polyurethane resin can be obtained by reacting a diol such as the general formula (■) with a diisocyanate.

(HOCHZCH2h--N-→Y+-X -fH,h
-COOH.--(Vffl) Also, for example, a polyester resin can be obtained by reacting a diol as represented by the general formula (■) with a compound having acid chloride at both ends.

The acid value of the polymer of the present invention is 6.0 meq/g to 0.
01 meq/g is preferable, 2. Omeq/g～
0.1 meq/g is particularly preferred. 0.01 me
q/g, the developability with an alkaline developer decreases, and on the other hand, 6.0 ff1eQ/
This is because as it becomes higher than g, the film strength and adhesive force to the support decrease. Further, the carboxylic acid in these resins may additionally contain one that is not decarboxylated by light. Moreover, two or more types of groups containing carboxyl groups that are decarboxylated by light may be introduced into the same polymer.

The molecular weight of the polymer of the present invention is determined by gel permeation chromatography, and the weight average molecular weight is 2000.
~1 million is appropriate, but preferably 8000~20
Ten thousand. This is because as the number becomes smaller than 8,000, the image strength decreases, and as the number becomes larger than 200,000, the developability decreases.

Furthermore, two or more of the above polymers may be used, or the above polymer may be mixed with another polymer having a carboxyl group that is not decarboxylated by light.

In this case, the proportion of other polymers that can be mixed is 95% by weight or less based on the total photosensitive composition. This is because as the amount of other polymers increases above 95% by weight, the benefits of using the polymer according to the invention decrease. Examples of other polymers to be mixed include polyamide resins, epoxy resins, polyurethane resins, acrylic resins, polyester resins, and polyvinyl acecool resins.

Examples of the diazonium compound used in the present invention include the diazonium compounds described in U.S. Pat. No. 3,867,147 and the diazonium compounds described in U.S. Pat. For example, diazo resins represented by condensates with formaldehyde are useful.

Preferred diazo resins include, for example, hexafluorophosphates, tetrafluoroborates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, U.S. Patent No. 330030
Sulfonates of condensates of p-diazodiphenylamine and formaldehyde as described in No. 9 (e.g., p-toluenesulfonates, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonates, etc.)
, phosphinates (eg, benzene phosphinates), hydroxy group-containing compound salts (eg, 2,4-dihydroxybenzophenone salts), organic carboxylates, and the like are also preferred.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4,4
Mesitylene sulfonate obtained by condensation with '-bis-methoxy-methyl-diphenyl ether is also suitable.

The amount of these diazonium compounds added to the total photosensitive composition is preferably 1 to 5% by weight, more preferably 3% by weight.
~15% by weight. If it is less than 1% by weight, the adhesion to the support will not be improved, while if it is more than 50% by weight, the film quality will deteriorate.

In the present invention, sensitivity can also be increased by adding a photosensitizer. Examples of the photosensitizer used in the present invention include xanthone, fluorenone, benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2.4
-diethylthioxanthone, acetophenone, naphthylacetone, 4.4'-bisdimethylaminobenzophenone, trinitrofluorenone, dibenzosuberone, 2.
Aromatic ketone compounds such as 5-bis-(4'-diethylaminobenzal)cyclopentanone, α,α-dichloro-4-phenoxyacetophenone, and 1-hydroxycyclohexylphenyl ketone; 4,4'-bisdimethylaminothiobenzophenone Aromatic thioketone compounds such as benzoquinone, dichlorobenzoquinone, tetrachlorobenzoquinone, dichlornaphthoquinone, anthraquinone, phenanthrenequinone, dichloroanthraquinone,
Quinone compounds such as dinitroanthraquinone, alizarin, and benzanthraquinone; aromatic nitro compounds such as nitrobenzene, 1-nitronaphthalene, 4-nitrobiphenyl, 4-nitrotoluene, 1,3-dinitrobenzene, and 2.4.6-trinitroaniline; Compounds: Aromatic hydrogen oxides such as naphthalene, anthracene, phenanthrene, benzanthracene, benzpyrene; triarylpyrazoline compounds such as triphenylvirazoline; monoimidazole compounds such as tetraphenylimidazole and triphenylimidazole; fluorescein, eosin Y10 - Zubenganopoe'J) Rosin B1 Xanthine compounds such as phloxine 1 Acriflavin, riboflavin, acridine, 9-phenylacridine, N-phenylacridine, phenazine, 2,3-diphenylquinoxaline, acenaphtho(1,2-b)quinoxaline, etc. Acridine-based compounds; 7-N,N-diethylami-7ketocoumarin, 3-benzoyl-7-ethylaminocoumarin, 3-benzoyl-7-medoxycoumarin, 3
．． Coumarin-based compounds described in U.S. Patent No. 4.289.844, such as 3'-carbonylbis(7-dinithylaminocoumarin); triphenylmethane-based compounds, such as thymol blue, bromothymol blue, and bromcresol green; ; Quinazolinone compounds such as 2-methyl-3-benzenesulfonyloxy-4(3H)-quinazolinone, 2-(β-styryl)-3-benzenesulfonyloxy-4(3H)quinazolinone, and the like. Two or more of the above sensitizers can also be used in combination.

The photosensitizer is 0.01 to 50% of the total photosensitive composition.
It is preferable to add it in an amount of 0.1 to 30% by weight, especially 0.1 to 30% by weight. This is because if it is less than 0.1% by weight, the effect of adding it will be small, and if it is more than 30% by weight, the film strength will decrease and the sensitivity will also decrease.

Furthermore, a polymerizable compound having an ethylenically unsaturated bond may be added to the present invention, if necessary. A polymerizable compound having such an ethylenically unsaturated bond is
A compound having at least one ethylenically unsaturated bond in its chemical structure, which includes monomers, prepolymers,
That is, it has chemical forms such as dimers, trimers, other oligomers, mixtures thereof, and copolymers thereof. Examples thereof include unsaturated carboxylic acids and their salts, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid,
These include maleic acid.

Salts of unsaturated carboxylic acids include alkali metal salts of the aforementioned acids, such as sodium and potassium salts.

Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate), 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. Acrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di pentaerythritol diacrylate,
Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,
Examples include polyester acrylate oligomers. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol dimethacrylate. Erythritol trimetaph IJL/-), dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p-(3-methacryloxy-2-hydroxypropoxy)phenylfudimethylmethane, bis-(:
Examples include p-(methacryloxyethoxy)phenylfudimethylmethane. Examples of itaconic acid esters include ethylene glycol shiitaconate, propylene glycol shiitaconate, 1,3-butanediol shiitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, and pentaerythritol shiitaconate. , sorbitol tetrataconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of incrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diincrotonate, and sorbitol tetraisocrotonate. Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.

Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1.6-hexamethylenebis-methacryl. amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

As another example, the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group as shown in IX) is added.

CH2=C(R)COOCH2CH(R')OH(IX
) (However, R and R' represent H or CH3.

) The above-mentioned polymerizable compound having an ethylenically unsaturated bond is preferably added in an amount of up to 90% by weight, particularly up to 60% by weight, based on the total photosensitive composition. If the amount is more than 60% by weight, the plate has the disadvantage of being sticky.

The photosensitive composition of the present invention may contain dyes, pigments,
Stabilizers, fillers, surfactants, plasticizers, antifouling agents,
Performance can also be improved by adding a fat-sensitizing agent or the like. Suitable dyes include oil-soluble dyes such as C01,26
105 (Oil Red RR), C01,21260 (Oil Blue Let #308), C01,74350 (Oil Blue), C,I, 52015 (Methylene Blue), C01,42555 (Crystal Violet'), C,1,42595 ( Victoria Pure Blue).

The photosensitive composition of the present invention is usually used by dissolving it in a solvent, applying it to a suitable support, and drying it.

The coating amount is approximately 0.01 to 500 g/m' in terms of dry weight.
Preferably it is 0.1 to 200 g/m'.

Examples of the solvent include methanol, ethanol, isoprobanonopenic n-butanol, t-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate, ethylene glycol, tetrahydrofuran, dioxane, dimethyl sulfoxide, N,
N-dimethylformamide, acetone, methyl ethyl ketone, 1-methoxy-2-propatol, 2-methoxy-1-propane, l-methoxy-2-acetoxypropane, 2-methoxy-1-acetoxypropane, ethyl acetate, methyl acetate , toluene, xylene, etc. and mixtures thereof are used.

Examples of the support to which the photosensitive composition of the present invention is applied include paper, paper laminated with plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), e.g. aluminum (including aluminum alloy),
Plates of metals such as zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic films laminated with or vapor-deposited with metals such as those mentioned above. Among these supports, when used as a printing plate, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive.

Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film described in Japanese Patent Publication No. 48-18327 is also preferred.

In the case of supports with a surface of metal, especially aluminum, electrolytic graining, composite graining, graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodizing. It is preferable that surface treatment such as surface treatment is performed. Preferred anodizing treatments include high current density anodization in sulfuric acid as described in British Patent No. 1,412,768 and as described in U.S. Pat. No. 3,511,661. A method of anodizing phosphoric acid in an electrolytic bath, a method of anodizing in a mixed acid of phosphoric acid and sulfuric acid as described in Japanese Patent Publication No. 46-43124, Japanese Patent Publication No. 52-103208, and Japanese Patent Publication No. 55-28400. is included.

In addition, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution, and an aluminum plate that has been anodized as described in Japanese Patent Publication No. 47-5125 and then immersed in an aqueous solution of an alkali metal silicate. A treated material or a material obtained by anodizing an aluminum plate and then treating it with an aqueous polyvinylphosphonic acid solution as described in Japanese Patent Publication No. 4G-35685 are also preferably used.

The above-mentioned anodizing treatment may be performed using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either 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.

Further, it is also preferable to perform graining treatment, anodization, and then sealing treatment. The sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like, followed by development with an aqueous developer, provides a negative relief image on the original.

Light sources used for exposure include, but are not limited to, carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, argon lasers, and excimer lasers.

The polymers of the present invention are primarily used as printing plate and resist materials.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Note that % in the examples means % by weight unless otherwise specified.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

(Synthesis Example 1) Synthesis of (A) 17.6 parts by weight of m-aminomethacrylanilide, 6.9 parts by weight of potassium carbonate, 2 parts by weight of N,N-dimethylformamide
5 parts by weight of the mixture was stirred, and 16.7 parts of ethyl bromoacetate was added dropwise while cooling the mixture to 0°C or lower. After dripping, 3
After stirring at room temperature for an hour, 80 parts by weight of water was added to the mixture and extracted with ethyl acetate. Next, the ethyl acetate layer was washed with diluted hydrochloric acid, washed with saturated saline, and then dried over magnesium sulfate. Next, it was concentrated using an evaporator, and the obtained solid was recrystallized with methanol.
．． 0 parts by weight of a compound (B) having the structural formula (B) was obtained.

After 15.0 parts by weight of compound (B) was dissolved in 20 parts by weight of ethanol and cooled on ice, a solution of 2.3 parts by weight of sodium hydroxide/60 parts by weight of water was added dropwise thereto.

After stirring at 20°C for 30 minutes, washing with ethyl acetate was carried out.
Furthermore, an aqueous solution of IN in hydrochloric acid was added to obtain 1) H2, and washing with ethyl acetate was performed. Next, an aqueous IN sodium hydroxide solution was added to bring the aqueous layer back to pH 3, and the mixture was extracted with ethyl acetate. After drying with magnesium sulfate, it was concentrated using an evaporator to obtain a compound (C) with structural formula (C) of 9.0
Part by weight obtained.

Under a nitrogen atmosphere, 2.34 parts by weight of compound (C) and 10.28 parts by weight of ethyl methacrylate were mixed with methyl cellosolve 3.
After dissolving in 8.0 parts by weight, stirring and heating to 70°C, 0.164 parts by weight of azobisisobutyronitrile (AIBN) was added, stirred for 5 hours, further stirred at 85°C for 3 hours,
A polymer (A) having a weight average molecular weight of 58.000 was obtained.

(Synthesis Example 2) 1.6 parts by weight of sodium hydroxide was dissolved in ethanol,
A solution of 5 parts by weight of p-aminothiophenol dissolved in 20 parts by weight of ethanol was added to the solution. Next, the obtained mixture was cooled to below 0°C, and a solution of 3.8 parts by weight of chloroacetic acid and 3.4 parts by weight of hydrogen carbonate dissolved in 10 parts by weight of water was added to the mixture. It was added dropwise while keeping the temperature below ℃. After dropping, stirring was carried out at 0°C for 3 hours, and then p
H was adjusted to 3, and the precipitated solid was filtered to obtain 5.4 parts by weight of p-aminothiophenoxyacetic acid.

5 parts by weight of p-aminothiophenoxyacetic acid, 2.
7 parts by weight were dissolved in 40 parts by weight of DMF, and 3.2 parts by weight of methacrylic acid chloride was added dropwise at 0°C or lower. 0℃ after dropping
The mixture was stirred at 25° C. for 1 hour, and further stirred at 25° C. for 2 hours. Then p
The obtained reaction solution was added to 500 parts by weight of an aqueous solution of H1 in hydrochloric acid, and extracted with ethyl acetate. Next, the ethyl acetate layer was dried with magnesium sulfate and concentrated, and the obtained crystals were recrystallized with ethyl acetate to obtain a compound (E) having the following formula (E).
1.26 parts by weight of was obtained.

Under a nitrogen atmosphere, 1.26 parts by weight of compound (E) and 5.14 parts by weight of ethyl methacrylate were dissolved in 25 parts by weight of methyl cellosolve, stirred, and heated at 70°C for 5 hours.
The mixture was stirred at 0° C. for 3 hours to obtain a polymer (D) having a weight average molecular weight of 400.00.

(Synthesis Example 3) 20.8 parts by weight of polystyrene with a weight average molecular weight of 10,000 and 13.5 parts by weight of ethyloxa dichloride were dissolved in 500 parts by weight of carbon disulfide, and while stirring, 18.22 parts by weight of aluminum chloride was dissolved. Added gradually. Next, the resulting mixture was stirred under reflux for 1.5 hours, and then 70% of the charged carbon disulfide was distilled off, and the residue was poured into a mixture of 40 parts by weight of concentrated hydrochloric acid and 100 parts by weight of ice. I put it in. After decantation, water was further added and the remaining solid was dissolved in acetone, reprecipitated in methanol, and the solid was filtered to obtain 11.5 g of polymer (G).

Next, after dissolving 10 parts by weight of polymer (G) in 600 parts by weight of THF, 50 parts by weight of an aqueous solution of IN (IN) was added.
parts by weight and 150 parts by weight of water were added, and the mixture was refluxed for 2 hours.

After the reaction, 28.8 parts by weight of acetic acid was added, reprecipitated in methanol, and dried to obtain 4.0 parts by weight of polymer (F).

(Synthesis Example 4) 82.34 parts by weight of the compound synthesized in Synthesis Example 1 and 5.04 parts by weight of allyl methacrylate were dissolved in 50.06 parts by weight of methyl cellosolve, and the mixture was stirred for 70 minutes under nitrogen atmosphere.
After heating to .degree. C., 0.186 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and the mixture was reacted for 4 hours, followed by reprecipitation in hexane.

Through the above process, 5.1 g of the following polymer (H) was obtained.

The weight average molecular weight was 20,000.

Examples 1 to 8, Comparative Examples 1 to 4 The surface of an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and a 400 mesh aqueous suspension of pumice stone, and then thoroughly washed with water. This is 1
After etching by immersing in IJum aqueous solution (0% hydroxide) at 70°C for 60 seconds, washing with running water, and neutralizing with 20% nitric acid, the surface was electrochemically roughened as described in JP-A-53-67507. Converting method, i.e. ■E = 12.7 V, Vo = 9
．． Using an IV sinusoidal alternating waveform current, electrolytic surface roughening treatment was carried out in a 1% sulfuric acid aqueous solution with an anode special electricity amount of 160 corons/dm.Subsequently, the surface was immersed in a 30% sulfuric acid aqueous solution. After desmutting for 2 minutes at °C, it was anodized in a 7% sulfuric acid aqueous solution to a thickness of 2.0 g/m'.Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 °C for 1 minute. treated, washed with water and dried.

Photosensitive solutions Nα, (1) to α shown in Table 1 were applied to the aluminum plate obtained as described above using a boiler, and dried at 80° C. for 2 minutes. Dry weight is 2.0 g
/ m'.

The diazoniums (a), wa), and (C) used are as follows.

Diazonium compound (a): PF, salt of a condensate of 4-diazodiphenylamine and formaldehyde.

Diazonium Compounds]; Dodecylbenzenesulfonate of a condensate of 4-diazodiphenylamine and formaldehyde.

Diazonium compound (C): 3-methoxy-4-diazo-diphenylamine and 4,4
Mesitylene sulfonate of condensate with '-bis-methoxy-methyl-diphenyl ether.

The photosensitive lithographic printing original plate thus obtained was image-exposed for 5 minutes using a PS light manufactured by Fuji Photo Film ■ through a step wedge from a distance of 1 m.
After soaking for a minute, rinse with water while scrubbing with an underwater sponge.
The unexposed area was removed.

Developer formulation: Sodium sulfate 5g benzyl alcohol 30g sodium carbonate
5g Isopropylnaphthalene 12g Sodium sulfonate water 1000g The presence or absence of image formation in the exposed area was as follows.

Table 2: Presence of image formation According to Table 2, the addition of a diazonium compound improves the adhesion between the support and the photosensitive layer, and the image in the exposed area does not come off from the support even when rubbed with a sponge during development. It can be seen that an image is formed.

Claims (5)

[Claims] (1) A photosensitive composition comprising a diazonium compound and a polymer having a carboxyl group-containing group that undergoes decarboxylation upon exposure in the presence or absence of a sensitizer. (2) The carboxyl group-containing group has the following general formula (
I) The photosensitive composition according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (In the formula, X means sulfur, oxygen, single bond, ■C=W or ■NU-U, and W means oxygen, sulfur. However, U means an aryl group, alkyl group, or hydrogen atom that may have a substituent, Y means an alkylene, arylene, aralkylene, or divalent heterocycle that may have a substituent, and K is 0
or 1, and l is 0 or 1) (3) The photosensitive composition according to claim 2, wherein the polymer has the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, X means sulfur, oxygen, single bond, ■C=W or ■NU-U, and W means oxygen, sulfur. , U means an aryl group, alkyl group, or hydrogen atom which may have a substituent, Y means an alkylene, arylene, aralkylene, or divalent heterocycle which may have a substituent, and P means Z means the polymer main chain, and Z means the polymer main chain and the above general formula (
A group that connects with the group I), such as an ether bond, amide bond, ester bond, urethane bond, ureido bond,
or contains them, K is 0 or 1, l is 0 or 1, m is 0 or 1, and n is the acid content of the polymer from 0.01 (meq/g) to 6.0.
(meq/g). ). (4) The photosensitive composition according to any one of claims 1 to 3, which contains the sensitizer. (5) Claims 1 to 3 contain a monomer having a polymerizable ethylenically unsaturated bond.
The photosensitive composition according to any one of Item 4.