JPH02156241A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve wear resistance and chemical resistance by incorporating a polyurethane resin which has a sulfonamide group in the main chain, is insoluble in water and is soluble in an aq. alkaline soln. and a photosensitive compd. which acts on a positive type. CONSTITUTION:This photosensitive compsn. contains the polyurethane resin which has the sulfonamide group in the main chain, is insoluble in water and is soluble in the aq. alkaline soln. and the photosensitive compd. which acts on the positive type. The mol.wt. of the polyurethane resin is >=2,000 in weight average and >=1,000 in number average and the photosensitive compd. which acts on the positive type includes more specifically an o-naphthoquinone diazide compd. The alkali soluble high-polymer compd. is used at the addition rate of <=70wt.% of the total compsn. The ratio of the photosensitive compd. which acts on the positive type and occupies in the photosensitive compsn. is 10 to 50wt.%, more preferably 15 to 40wt.%. The wear resistance and chemical resis tance are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive composition suitable for the production of lithographic printing plates, IC circuits and photomasks, and more particularly, to photosensitive compositions suitable for the production of lithographic printing plates, IC circuits and photomasks, and more particularly, to photosensitive compositions suitable for the production of lithographic printing plates, IC circuits and photomasks. and a photosensitive composition comprising a polymer compound with excellent abrasion resistance and chemical resistance.

[Conventional technology]

A photosensitive composition comprising an O-naphthoquinone diazide compound and a novolac type phenol resin as a binder has been used industrially as an extremely excellent photosensitive composition in the production of lithographic printing plates and as a photoresist. However, due to the nature of novolac type phenolic resin, it has poor adhesion to the substrate, the film is brittle, and the coating properties are poor.
Points that should be improved include poor abrasion resistance and insufficient stiffness resistance when used in lithographic printing plates, poor chemical resistance, and especially insufficient stiffness resistance when used with UV ink. There is. Burning treatment (heat treatment after exposure and development) is generally used to improve these various properties.

However, when the burning process is performed, there is a problem in that low-molecular compounds in the photosensitive layer adhere to non-image areas rather than image areas, making it easier to cause stains during printing.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Although the polyhydroxystyrene or hydroxystyrene copolymer described in No. 1050 did have improved film properties, it had the disadvantage of poor abrasion resistance and chemical resistance. Furthermore, in JP-A-51-34711, it is proposed to use a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder; There were problems such as a narrow range and insufficient wear resistance.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition in which a polymer compound used as a binder has excellent abrasion resistance, can be developed with an aqueous alkaline developer, and provides a lithographic printing plate with high printing durability. .

Another object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate with high printing durability even when printed with UV ink without chemical resistance (or burning treatment). It is in.

A further object of the present invention is to provide a photosensitive composition that has good adhesion to a substrate, provides a flexible film, and has excellent solubility in organic solvents.

[Structure of the Invention] As a result of intensive study by the present inventors to achieve the above object,
It has been found that the above objects can be achieved by using a novel photosensitive composition using a specific binder,
We have arrived at the present invention.

That is, the present invention provides a photosensitive material containing a polyurethane resin having a sulfonamide group in its main chain, insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound acting in a positive tone. Regarding the composition.

The present invention will be explained in detail below.

The sulfonamide group present in the polyurethane resin of the present invention is a sulfonamide group in which one H is bonded to nitrogen (S(h
NH).

The polyurethane resin having a sulfonamide group in the main chain that is preferably used in the present invention is a polyurethane resin whose basic skeleton is a reaction product of a polyol compound having one or more sulfonamide groups in the molecule and a polyisocyanate compound. It is resin.

The polyurethane resin having a sulfonamide group that is more preferably used in the present invention is a reaction product of a diol compound having a sulfonamide group and a diisocyanate compound represented by the following formulas (1) and (II). The basic skeleton is polyurethane resin.

a C1-Cat alkylene group, a cycloalkylene group, which represents a valent linking group, and preferably has a substituent;
Indicates an aralkylene group or an arylene group.

k, l, m and n each represent an integer of 0 or more, preferably O or 1. However, k+4! +Q, m+
n'pO.

-1 Specific compounds represented by formula (I) or (II) include, for example, compounds represented by the following structural formula.

R1, RZ, R1, R4, R5 and Rh may be the same or different, and each of these sulfonamide groups is composed of two or more atoms selected from C, H, N, 0 and S. These diol compounds can be used alone or in combination of two or more.

Further, a diol compound that does not have a sulfonamide group and may have other substituents that do not react with isocyanate can also be used in combination.

Specifically, such diol compounds include those shown below.

Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1.3-butylene gellicol, 1.
6-hexanediol, 2-butene-1,4-diol, 2゜2.4-)dimethyl-1,3-bentanediol, 1.4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclo Decane dimetatool, hydrogenated bisphenol A1 hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p -xylylene glycol,
Dihydroxyethyl sulfone, bis(2-hydroxyethyl)-2,4-1-lylene dicarbamate, 2,4-
) rylene-bis(2-hydroxyethyl rubamide),
Bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl)isophthalate 3.5-dihydroxybenzoic acid, 2.2-bis(hydroxymethyl)propionic acid, 2.2-bis(2 -hydroxyethyl)propionic acid, 2゜2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid a, bis(4-hydroxyphenyl)acetic acid, 4
．． Examples include 4-bis(4-hydroxyphenyl)pentanoic acid and tartaric acid.

Specifically, the diisocyanate compounds preferably used in the present invention include those shown below.

That is, 2.4-)lylene diisocyanate, a dimer of 2°4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-
Aromatic diisocyanate compounds such as xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3°3′-dimethylbiphenyl-4,4′-diisocyanate; Hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate,
Aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4,4'
-methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2.6) diisocyanate, ■.

Alicyclic diisocyanate compounds such as 3-(isocyanatomethyl)cyclohexane; reaction of diols and diisocyanates such as adducts of 1 mole of 1,3-butylene gellicol and 2 moles of tolylene diisocyanate; Examples include diisocyanate compounds, which are compounds.

The polyurethane resin of the present invention is prepared by adding the above-mentioned diisocyanate compound and diol compound in an aprotic solvent, if necessary, adding a known catalyst having an activity corresponding to each reaction.
Synthesized by heating. The molar ratio of the diisocyanate and diol compound used is preferably 0.8:
1 to 1.2:1, and if an isocyanate group remains at the end of the polymer, it is finally synthesized in a form in which no isocyanate group remains by treatment with alcohols or amines.

The polyurethane resin of the present invention preferably has a weight average molecular weight of 2. OO0 or more, and the number average is 1,000 or more. More preferably, the weight average is 5,000 to 30
The average number ranges from 20,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 1O.

The polyurethane resin used in the present invention may be used alone or in combination. The content of this polyurethane resin in the photogenic composition is about 5 to 95%, preferably about 10%. ~85%.

A specific example of the positive-acting photosensitive compound used in the present invention is an O-naphthoquinone diazide compound.

The O-naphthoquinone diazide compound used in the present invention is preferably an ester of 1,2-diazonaphthoquinone sulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 43-28403, and others. Suitable orthoquinonediazide compounds include those described in U.S. Pat.
．． 1,2- described in No. 188.210
There are esters of diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins. Other useful 0-naphthoquinone diazide compounds are known and reported in numerous patents. For example,
No. 7-5303, No. 63802, No. 48-1973, No. 7-5303, No. 63802-
No. 63803, No. 96575 of 1973, No. 3 of 1972
No. 8701, No. 13354 of 1972, Special Publication No. 1 of 1972
No. 8015, No. 11222, No. 41-1122, No. 11222, No. 45-96.
No. 10, Publication No. 49-17481, U.S. Patent No. 2.
No. 797.213, No. 3.454.400, No. 3
．． 544.323, British Patent No. 3, 573.917, British Patent No. 3.674.495, British Patent No. 3.785.825, British Patent No. 1.227.602, British Patent No. 1.251.34
No. 5, No. 1.267, 005, No. 1.329.8
No. 88, No. 1, 330.932, German Patent No. 85
Examples include those described in various specifications such as No. 4.890.

A particularly preferred 0-naphthoquinone diazide compound in the present invention is a compound obtained by reacting a polyhydroxy compound with a molecular weight of 1.0 Oa or less and 1,2-diazonaphthoquinone sulfonic acid chloride. Specific examples of such compounds are disclosed in JP-A-51-139402 and JP-A-51-5B.
-150948, 58-203434, 59-
No. 165053, No. 60-121445, No. 60-1
No. 34235, No. 6Q-163043, No. 61-11
No. 8744, No. 62-10645, No. 62-1064
No. 6, No. 62-153950, No. 62-178562
No. 62-233292, U.S. Patent No. 3.10
No. 2,809, No. 3.126,281, No. 3.1
30.047, 3.148.983, 3.
184.310, 3.188.21Q, 4
．． Examples include those described in various publications or specifications such as No. 639.406.

When synthesizing these 0-naphthoquinone diazide compounds, 1
．． 0.2 of 2-diazonaphthoquinone sulfonic acid chloride
It is preferable to react by 1.2 equivalents, and more preferably 0.3 to 1 equivalent.
．． It is preferable to carry out the reaction in an amount of 0 equivalent.

The obtained 0-naphthoquinonediazide compound has 1.2-
Although it is a mixture of diazonaphthoquinone sulfonic acid ester groups having various positions and amounts of introduction, the proportion of compounds in which all hydroxyl groups have been converted with 1,2-diazonaphthoquinone sulfonic acid ester in this mixture is 5 mol% or more. is preferable, more preferably 2
It is 0 to 99 mol%.

As a photosensitive compound that acts positively without using an 0-naphthoquinonediazide compound, for example, Japanese Patent Publication No. 56-26
Polymeric compounds having orthonitrocarbinol ester groups as described in No. 96 can also be used in the present invention.

In addition, there are compounds that generate acid by photolysis, and compounds that generate GI by photolysis.
Combination systems with compounds having a 1c-oc-c group or a 1t-C-0-3i group can also be used in the present invention.

For example, a combination of a compound that generates an acid by photolysis and an acetal or an O,N-acetal compound (JP-A-48-1999-1)
89003), a combination with an orthoester or amide acetal compound (JP-A-51-120714), a combination with a polymer having an acetal or kecool group in the main chain (JP-A-53-133429), and an enol ether compound. combination (JP-A-55-12995), N
- Combination with acylimino carbon compound (JP-A-55-1
26236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a silyl ester compound (JP-A-60-10247), and a combination with a silyl ether compound (JP-A-56-10247). 1986-
No. 37549, JP-A-60-121446), etc.

The amount of these positive-acting photosensitive compounds (including combinations as described above) in the photosensitive composition of the present invention is 10 to 50% by weight, more preferably 15 to 40% by weight.
It is.

In addition to the polyurethane resin having a sulfonamide group, the composition of the present invention contains phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m-/p-mixed cresol formaldehyde resin, phenol/cresol ( m-
Contains known alkali-soluble polymer compounds such as cresol formaldehyde resins such as mixed formaldehyde resins (either 1p-1 or m-/p-mix), phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. can be done. These alkali-soluble polymer compounds have a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200.
~60.000 is preferred.

Such alkali-soluble polymer compound accounts for 70% of the total composition.
It is used in an amount of less than % by weight.

Furthermore, as described in U.S. Pat. No. 4,123,279, phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, It is preferable to use a condensate with the above compound in combination to improve the oil sensitivity of the image.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As a cyclic acid anhydride, US Pat. No. 4.115.
128, phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride There are acids etc. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times.

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of O-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223 and JP-A-54-74728
No. 60-3626, No. 61-143748, No. 61-151644, No. 63-58440, the combination of trihalomethyl compound and salt-forming organic dye can be mentioned. In addition to the salt-forming organic dyes mentioned above, other dyes can also be used as colorants. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #130.
Oil pink #312, oil green BG, oil blue BO3, oil blue #603, oil black B
Y, Oil Black BS, Oil Black T-505 (
(manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555)
), Methyl Violet (CI 42535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (CI52015)
) can be mentioned. Also, JP-A-62-2932
The dyes described in Publication No. 47 are particularly preferred.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, l-methoxy-2-propanol, l
-Methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, Examples include isopropanol and diethylene glycol dimethyl ether, and these solvents can be used alone or as a mixture. The concentration (solid content) of the above components is preferably 2 to 50% by weight, and the coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3. 0 g/d is preferable; as the coating amount becomes thinner, the photosensitivity increases; however,
The physical properties of the photoresist film deteriorate.

In the composition of the present invention, a surfactant for improving coating properties, such as a fluorine-containing surfactant as described in JP-A-62-170950, can be added. A preferable addition amount is 0.01 to 0.01 of the total photosensitive composition.
1% by weight, more preferably 0.05-0.5% by weight.

When producing a lithographic printing plate using the photosensitive composition of the present invention, an aluminum plate is preferable as the support.

Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, such as alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, 11:'smuth, and nickel. These compositions contain some iron and titanium as well as other negligible impurities.

The aluminum plate is surface-treated as necessary. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment is preferably performed. Aluminum plate grained and immersed in an aqueous sodium silicate solution, as described in U.S. Patent No. 3.1
81.461, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodic oxidation treatment may be performed using an electric field using 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, alone or in combination. This is carried out by passing an electric current through a liquid using an aluminum plate as an anode.

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

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. This is done to improve the quality of life.

Prior to graining the aluminum plate, if necessary, the surface may be pretreated to remove rolling oil and expose a clean aluminum surface; for the former, Solvents such as trichlorethylene, surfactants, etc. are used. For the latter, a method using an alkaline etching agent such as sodium hydroxide or potassium hydroxide is widely used.

Mechanical, chemical, and electrochemical methods are all effective for graining. Mechanical methods include ball polishing, plastic polishing, and water-dispersed slurry of abrasives such as pumice. There is a brush polishing method in which the material is rubbed with a nylon brush, and chemical methods include
A method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Publication No. 31187 is suitable.
As the electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid, or a combination thereof is preferred.
Among these surface roughening methods, especially Japanese Patent Application Laid-Open No. 55-1379
A surface roughening method that combines mechanical roughening and electrochemical roughening as described in Japanese Patent No. 93 is preferred because it provides strong adhesion of the oil-sensitive image onto the support.

Graining by the method described above is preferably carried out in such a range that the centerline surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μ.

The thus grained aluminum plate is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous base or acid solutions that dissolve aluminum. In this case, the etching agent must not form a film different from aluminum derived from the etching solution components on the etched surface. Examples of preferred etching agents include sodium hydroxide, potassium hydroxide, Trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate, etc.; examples of acidic substances include sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid, and their salts, but metals with a lower ionization tendency than aluminum, such as Salts of zinc, chromium, cobalt, nickel, copper, etc. are not preferred because they form unnecessary films on the etched surface.

These etching agents have a dissolution rate of 0.3 to 40 g/r+ per minute of immersion time for the aluminum or alloy used, depending on the concentration and temperature settings. It is most preferable to do it so that it is, but it may be more or less than this.

Etching is performed by immersing the aluminum plate in the above etching solution or applying the etching solution to the aluminum plate, and the etching amount is 0.5 to 10 g/r.
+? It is preferable that the treatment be carried out so that it falls within the range of .

As the above-mentioned etching agent, it is preferable to use an aqueous base solution because of its high etching rate.In this case, since smut is generated, desmutting is usually performed. Acids used for desmutting include nitric acid,
Sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoroboric acid, etc. are used.

The etched aluminum plate is washed with water and anodized if necessary. Anodic oxidation can be performed by methods conventionally practiced in this field. Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid,
When direct current or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing benzenesulfonic acid or the like or a combination of two or more thereof, an anodic oxide film can be formed on the surface of the aluminum support.

The processing conditions for anodic oxidation vary depending on the electrolytic solution used, so it cannot be determined exactly, but in general, the electrolytic solution concentration is 1 to 80% by weight, the solution temperature is 5 to 70°C, and the current density is 0.
．． A suitable range is 5 to 60 amperes/dm2, voltage 1 to 100 V, and electrolysis time 30 seconds to 50 minutes.

Among these anodizing treatments, the British Patent No. 1.
412.768, a method of anodizing at high current density in sulfuric acid, U.S. Pat. No. 4,211.6.
The method of anodizing in low concentration sulfuric acid as described in US Pat. No. 3,511,661 and the method of anodizing using phosphoric acid as an electrolytic bath are preferred.

The aluminum plate roughened as described above and further anodized may be subjected to a hydrophilic treatment if necessary. Preferred examples include U.S. Pat. Nos. 2.714.066 and 3.181 Alkali metal silicates, such as aqueous sodium silicate solutions, as disclosed in Japanese Patent Publication No. 36-22063, and potassium fluorinated zirconate as disclosed in Japanese Patent Publication No. 36-22063, and U.S. Pat. No. 4.153.4.
There is a method of treating with polyvinylsulfonic acid as disclosed in No. 61.

Further, an undercoat layer made of a water-soluble compound can be provided on the aluminum plate which has been roughened as described above, anodized, and further subjected to a hydrophilic treatment if necessary. Examples of such water-soluble compounds include Japanese Patent Publication No. 57-16349.
Combinations of water-soluble metal salts and hydrophilic cellulose (e.g., zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose, etc.) disclosed in U.S. Patent No. 3,511.661 Polyacrylamide, Special Publication Showa 46-356
Polyvinylphosphonic acid disclosed in Japanese Patent Publication No. 85, amino acids and their salts (alkali metal salts such as Na salt and K salt, ammonium salt, hydrochloride, oxalate, acetate, phosphate, etc.)
, hydroxyl group-containing amines and their salts (hydrochloride, oxalate,
phosphates, etc.), among which amino acids and their salts,
Amines and their salts having hydroxyl groups are particularly preferred.The undercoat layer of such water-soluble compounds has a solid content of 1 to 80 μ/d.
It is preferable to set it within the range of .

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic diphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium chloride, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, with concentrations ranging from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight. It is added as follows.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary.

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

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent coating properties when applied onto a support, and also excellent developability when using an aqueous alkaline developer in the exposed area after coating, drying, and image exposure. The relief image obtained has good abrasion resistance and good adhesion to the support, and when used as a printing plate, many good prints can be obtained.

Furthermore, even when printing is performed using UV ink, a large number of good printed materials can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the content of the present invention is not limited thereto.

Synthesis Example 1 98.5 g of 0-aminobenzyl alcohol (Q,
13 mole) and 500 mI2 of acetone,
NaCI! - Stirred in an ice bath. In this flask, 27.5 g of m-benzenedisulfonyl chloride (0.1 s
ole) dissolved in 200 mf of acetone was added dropwise through a dropping funnel over about 1 hour. After completion of dripping NaC
I! - Removed the water bath and stirred at room temperature for 2 hours. After the reaction is completed, most of the acetone is distilled off under reduced pressure, and water II!
The mixture was added to the solution under stirring and further acidified with hydrochloric acid. The precipitate was collected by filtration and dissolved in an aqueous sodium hydroxide solution. After filtering off insoluble materials, the filtrate was placed in a separating funnel and washed twice with ethyl acetate.

The aqueous layer was made acidic by adding hydrochloric acid, and the precipitate was collected by filtration. By thoroughly washing with water and drying, NSN'
A solid of -bis(0-hydroxymethylphenyl)-m-benzenedisulfonamide was obtained (yield: 30.6 g).
).

Next, 100mJ equipped with a stirrer and cooling tube! In a three flask, 8.97 g of N,N'-bis(0-hydroxymethylphenyl)-m-benzenedisulfonamide
(0,02 sole), 4. 4'-diphenylmethane diisocyanate 5.26 g (0,021so
18 g of N, N-dimethylacetamide were added and stirred for 3 hours while heating to 80°C. After the reaction was completed, 10 g of methanol was added and stirred for a while, and the mixture was poured into 500 mJ of water with stirring and stirred for 30 minutes. . The precipitate was filtered and dried to obtain 14 g of white solid. The weight average molecular weight of this polymer compound (polystyrene standard) was determined by gel permeation chromatography.
was measured and found to be 55,000 (polymer compound (a) of the present invention).

Synthesis] to 1 The corresponding polyurethane resins (bl to (el) were synthesized by reacting the diisocyanate compounds and diol compounds shown in Table 1 in the same manner as in Synthesis Example 1.The weight average molecular weight of these polymer compounds ( polystyrene standard) were all 10,000 to 70,000.

The surface of an aluminum plate having a thickness of 1 to 5 mm and a thickness of 0.30 am was sanded using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water.

After etching by immersing it in 10% sodium hydroxide at 70° C. for 60 seconds, it was washed with running water, neutralized with 20% HNOx, and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with an anode special electric charge of 160 clones/da'' using a sinusoidal alternating current waveform under the condition of Va''12.7V. When the surface roughness was measured, it was 0.6μ (Ra display).Subsequently, it was immersed in a 30% UGSO* aqueous solution and desmutted at 55°C for 2 minutes.
Anodizing was performed in an aqueous ISOn solution at a current density of 2 A/da'' to a thickness of 2.7 g/rrl.

Next, by changing the type of polyurethane resin of the present invention in the following photosensitive composition (A), five types of photosensitive compositions (A) were prepared.
-1 to (A)-5 were adjusted.

These photosensitive compositions were applied onto an anodized aluminum plate and dried at 100° C. for 2 minutes to prepare photosensitive lithographic printing plates (A)-1 to (A)-5, respectively. The coating amount at this time was 2.5 g/nr in terms of dry weight.

The polyurethane resins of the present invention used in photosensitive compositions (A)-1 to (A)-5 are shown in Table 2.

Photosensitive composition [A]: Next, as a comparative example, the following photosensitive composition CB) was applied in the same manner as the photosensitive composition (A) to prepare a photosensitive lithographic printing plate (B). The coating weight after drying is 2.5g/n? Met.

Photosensitive composition [B]: Intermittent immersion development.

The obtained lithographic printing plates (A)-1 to -5 and (B) were printed on high-quality paper using a commercially available regular ink and UV ink using a KOR type printing machine manufactured by Heidelberg. The final number of printed sheets of lithographic printing plates (A)-1 to (A)-5 and (Bl) was examined and was as shown in Table 2.

A positive transparent original image of a line drawing and a halftone dot image is brought into close contact with the photosensitive planographic printing plates (A)-1 to -5 and the photosensitive layer of (B).
Exposures were made with a 0 amp carbon arc lamp from a distance of 70 CJ.

As shown in Table 2, the exposed photosensitive lithographic printing plates (A)-1 to -5 and (B) were heated with an 8-fold diluted aqueous solution of DP-4 (product name: Fuji Photo Film Side Type) at 25°C for 60 seconds. As,
Lithographic printing plate using polyurethane resin of the present invention [:A]
-1 to 5, (Examples 1 to 5) are lithographic printing plates [B] (
Compared to Comparative Example 1), the number of prints was large and the rigidity resistance was very excellent regardless of whether normal ink or UV ink was used.

Examples 6 to 9 and Comparative Example 2 After graining the surface of an aluminum plate with a thickness of 0.24 mm using a nylon brush and 400 mesh pumice stone in water suspension, the substrate [■] was thoroughly washed with water. Prepared. After etching the substrate [I] by immersing it in 10% sodium hydroxide at 70°C for 20 seconds, washing it with running water,
Neutralization cleaning with 0% HNO, washing with water, and electrolytic surface roughening treatment at 400 clones/dI112 in a 0.7% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of 12.7 V. The substrate [■] was prepared by washing with water.

This substrate (Il) was treated in a 10% aqueous sodium hydroxide solution so that the amount dissolved on the surface was 0.9 g/m''.

After washing with water, neutralize in 20% nitric acid solution, wash and desmut, and then wash in 18% sulfuric acid aqueous solution to reduce the amount of oxide film to 3.
Anodized to g/m'.

The following photosensitive compositions [3 types of photosensitive compositions CC in which the type of polyurethane resin of the present invention was changed in CD)-1 to [:CD-3] were placed on the aluminum plate thus obtained.
was applied. The plates were dried at 100° C. for 2 minutes to prepare photosensitive planographic printing plates (CD-1 to CD-3).

Furthermore, the following photosensitive compositions [D] and [E] were prepared, and C
C)-1 to [CD-3] were coated and dried to produce photosensitive planographic printing plates CD) and CE).

The coating weight of these photosensitive planographic printing plates after drying is 2.5g.
/m''.

In addition, photosensitive compositions (C)-1 to (CD-3 and CD)
The polyurethane resins of the present invention used in Table 3 are shown in Table 3.

Photosensitive composition [CD: '2.3.4-) Esterification of lyhydroxybenzophenone and naphthoquinone-1゜2-diazide-5-sulfonyl chloride 1 (esterification rate; 9Q+noj!%) O of the present invention Polyurethane resin 0 Cresol (60% meta form, 40% ortho form) - Formaldehyde resin (weight average molecular weight: 4.000) o2- (p-methoxyphenyl) 4.6-bis(trichloromethyl) -5-triazine 0 naphthoquinone -1,2-Diazide-sulfonyl chloride 0 Victoria Pure Blue BOH (dye manufactured by Hodogaya Chemical ■) Q Megafac F-177 (fluorinated surfactant manufactured by Dainippon Ink and Chemicals ■) 0, 45 g 0, 77 g 0,33 g 0,02 g 0.01g 0,015 g 0,004 g O dimethylformamide 01-methoxy-2-propatol O methyl ethyl ketone photosensitive composition [D]: 03.3.3', 3 Esterified product of '-tetramethyl-1,1'-spirobiindan-5,6,7,5',6'-7'-hexol and naphthoquinone-1,2-diazide-5-sulfonyl chloride (specially Photosensitive material (a) of Example 1 of Application No. 62-233292 O Polyurethane resin of the present invention O Cresol (60% meta form, 40% ortho form) - Formaldehyde resin (weight average molecular weight: 4.000) 02 -(p-methoxyphenyl) 4.6-bis(trichloromethyl) -8-triazine 0, 45 g 0, 77 g 0, 33 g 0, 02 g O Victoria Pure Blue B OH 0,015 g (Hodogaya Chemical Q@ O Megafafuku F -1770,004g (Fluorine surfactant manufactured by Dainippon Ink and Chemicals) 0Dimethyl sulfoxide 5go Methyl lactate 8go Methyl ethyl ketone 7g Photosensitive composition [E] Double photosensitive composition [C ], cresol (60% meta form, 40% ortho form) was used without using the polyurethane resin of the present invention.
%) - formaldehyde resin (weight average molecular weight; 4.0
A photosensitive solution using 1.1g of 00).

The performance of photosensitive lithographic printing plates (C)-1 to (C]-3, [D] and [E] was evaluated in the same manner as in Examples 1 to 5 and Comparative Example 1, and the results are shown in Table 3. It was uri.

As can be seen from Table 3, lithographic printing plates (C)-1 to (C)-3 and [D] using the polyurethane resin of the present invention
(Examples 6 to 9) have excellent printing durability and are very superior to the lithographic printing plate (E) (Comparative Example 2), regardless of whether normal ink or UV ink is used. .

Claims (1)

[Claims] A photosensitive composition comprising a polyurethane resin having a sulfonamide group in its main chain and being insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound that acts in a positive tone.