JPH0359666A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain proper developability at the time of being developed in an aqueous alkaline developing solution containing organic matter, such as an organic solvent and/or a surfactant, by incorporating 2 kinds of specified structural units in a photocrosslinkable polymer compound. CONSTITUTION:The photocrosslinkable polymer compound has the 2 kinds of structural units represented by formulae l and ll in which each of R<1> and R<6> is H, methyl, or halogen; R<2> is a divalent hydrocarbon group; R<3> is a divalent hydrocarbon group optionally having an ether, ester, or amido bond; each of R<4> and R<5> is H, 1 - 4 C alkyl, or halogen; X is -O- or -NH-; Y is an ether, ester, or amido bond; and Z is absent, or a divalent bonding group composed of >= 2 of C, H, N, and O, thus permitting proper developability to be obtained at the time of developing after exposure with the aqueous alkaline developing solution containing containing organic matter, such as an organic solvent and/or a surfactant.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive composition suitable for use in the production of lithographic printing plates, IC circuits, and photomasks, and in particular, the present invention relates to a photosensitive composition that is suitable for use in the production of lithographic printing plates, IC circuits, and photomasks. The present invention relates to a negative photosensitive composition containing a photocrosslinkable polymer compound having excellent properties.

[Prior art and problems to be solved] Photocrosslinkable materials that are crosslinked by cycloaddition reactions are well known, and many of these are used as main components of photosensitive compositions used in the production of photosensitive lithographic printing plates, etc. It is used. These photocrosslinkable polymer compounds include polymer compounds with maleimide groups in their side chains, cinnamyl groups with photodimerizable unsaturated double bonds adjacent to aromatic nuclei, cinnamyl IJden groups, chalcone groups, etc. in their side chains. Alternatively, a polymer compound having a main chain is useful, and a polymer compound having a maleimide group is particularly useful in terms of high sensitivity.

Negative photosensitive lithographic printing plates using these photocrosslinkable polymer compounds include an alkaline development type in which the unexposed area is removed (developed) with an aqueous alkaline developer, and an alkaline development type in which the unexposed area is removed (developed) in an organic solvent developer. Solvent development type is known, but from the viewpoint of occupational safety and health, alkali development type is preferable, and this is mainly determined by the properties of the photocrosslinkable polymer compound. Methods for imparting alkaline developability to photocrosslinkable polymeric compounds having maleimide groups are described in JP-A-52-988, JP-A-52-3055, JP-A-55-160010, etc. A method of obtaining a monomer having a maleimide group, a polymerizable double bond, and a carboxylic acid group in the molecule, as shown in FIG. A method of copolymerizing a monomer and a monomer having a carboxylic acid group and a polymerizable double bond in the molecule, or a method of copolymerizing a monomer having a carboxylic acid group and a polymerizable double bond in the molecule, or adding a maleimide group and a hydroxyl group or an amino group to a polymer compound having a carboxylic acid anhydride structure. There is a method of introducing a maleimide group while generating a carboxylic acid group by reacting a compound having the same. Among these, monomers having a maleimide group and a polymerizable double bond in the molecule and carboxylic acid groups in the molecule have the advantage that the content of maleimide groups and carboxylic acid groups in the polymer compound can be easily adjusted. A method of copolymerizing a monomer having a group and a polymerizable double bond is preferred.

On the other hand, when developing these negative photosensitive lithographic printing plates after exposure, the aqueous alkaline developer composition used is as follows:
For example, a developer composition consisting of benzyl alcohol, an anionic surfactant, an alkaline agent and water is disclosed in JP-A-51-77401, and JP-A-53-44202.
A developing solution composition consisting of an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite is described in JP-A No. 55-155355 and has a solubility in water at room temperature. 10% by weight in
Examples include the following developer compositions containing an organic solvent, an alkaline agent, and water.

All of these contain organic substances such as organic solvents and surfactants in their developer compositions. However, organic solvents have many drawbacks, such as -m being toxic and odorous, posing a risk of fire, and being subjected to BOD regulations even in waste liquid, and are also expensive. Furthermore, surfactants have the problem of generating bubbles during development, and it is desirable to use a developer composition that does not substantially contain these organic substances.

On the other hand, examples of developer compositions that do not substantially contain these organic substances include the developer composition described in Japanese Patent Application Laid-open No. 84241/1983.

However, these developer compositions are used when developing positive-working photosensitive lithographic printing plates containing an 0-naphthoquinone diazide compound as a photosensitive compound, and these developer compositions that are substantially free of organic matter are When the above-mentioned negative photosensitive lithographic printing plate is developed using the same method, it cannot be developed without producing a residual film, and proper developability cannot be obtained, and apparently proper developability cannot be obtained. Even in such cases, there is a problem in that stains occur in non-image areas when printing.

In the present invention, "substantially free of organic substances" means that the proportion of the substance in the composition is 3% by weight or less, preferably 1% by weight or less, from the above-mentioned safety point of view.
% by weight or less.

Therefore, an object of the present invention is to use a photocrosslinkable polymer compound with excellent solubility in an alkaline aqueous solution, so that it can be developed after exposure with an aqueous alkaline developer containing organic substances such as an organic solvent and/or a surfactant. Even when developed after exposure with an aqueous alkaline developer that provides appropriate developability and does not substantially destroy these organic substances,
It is an object of the present invention to provide a photosensitive composition which provides a lithographic printing plate that has appropriate developability and does not cause stains in non-image areas when printed.

[Means to solve the problem]

As a result of intensive study by the present inventors to achieve the above object,
The present inventors have discovered that these objects can be achieved by using a novel photosensitive composition, and have thus arrived at the present invention.

That is, the present invention provides a photosensitive composition containing a photocrosslinkable polymer compound, in which the photocrosslinkable polymer compound has a structural unit represented by the following - Funatsuri (I) and - formation (ff). It is structured so that it contains a structural unit that contains the following constituent units.

(In the formula, R1 and R6 each represent a hydrogen atom, a methyl group, or a halogen group, R2 represents a divalent hydrocarbon group, and R3 may have an ether bond, an ester bond, or an amide bond. represents a divalent hydrocarbon group, R4 and R5 each represent a hydrogen atom, a C3-C4 alkyl group, or a halogen group, R4 and R5 may be taken together to form a 5- or 6-membered ring, X represents 10- or -NH-, Y represents an ether bond, ester bond, or amide bond, and Z represents a single bond or a divalent group consisting of two or more atoms of C, HSN, and O. represents a linking group.

The present invention will be explained in detail below.

The photocrosslinkable polymer compound suitably used in the present invention has structural units represented by -formation (I) and (II),
It can be obtained by polymerizing monomers represented by the corresponding general formulas (■) and (TV), respectively, in an appropriate solvent using a known polymerization initiator.

) (In the formula, RI, R8 and X, Y and 2 have the same meanings as above.) Preferably, R1 or R6 is each a hydrogen atom or -CH3, and R2 is optionally branched C1 to C1 is an alkylene group or a phenylene group, R3 is a C2 to C86 alkylene group, an aralkylene group or a phenylene group which may have an ether, ester or amide bond, and R4 and R5 are -C1 or R4, respectively. R5 together form a 6-membered ring, and Z is preferably a single bond or a divalent linking group consisting of C, H, or O.

In the present invention, the general formula (III
Examples of monomers represented by ) include the following.

(In the formula, R', R' and R5 have the same meanings as above, R11 to Ras each represent a hydrogen atom or -CH, nl represents an integer of 2 to 20, and n2 to nl2 , an integer from 1 to 20) Examples of the compound represented by the general formula (IV) suitably used in the present invention include those shown below.

6 CH2=C diOOH 6 CH2=C COO-C112CH, -0-CD-CH, CH, -C
DDH (wherein R6 has the same meaning as above) The photocrosslinkable polymer compound suitably used in the present invention is:
A copolymer of one or more compounds represented by the above general formula (III) and one or more compounds represented by the general formula (TV), and further one or more polymerizable low-molecular compounds other than these. It may also be a multicomponent copolymer with more than one species.

Examples of such polymerizable low-molecular compounds include acrylonitrile, methacrylonitrile, acrylic esters, methacrylic ester acids, acrylamides,
Examples include methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonic acid esters.

Examples of solvents used in dissolving such polymeric compounds include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, -methoxy-2-propatool, 1-
methoxy-2-propylacetate), N,N-dimethylformamide, N,N'-dimethylacetamide,
Examples include toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and the like.

These solvents may be used alone or in combination of two or more.

The polymer compound of the present invention has an average of two or more photocrosslinkable groups per molecule in the side chain, and has a weight average molecular weight of preferably i, ooo or more, more preferably 2.000 or more.
The range is 300,000 to 300,000.

Further, the number average molecular weight is preferably 800 or more, and more preferably in the range of 1,000 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 10.

The polymer compound of the present invention may contain unreacted low-molecular compounds. In this case, the proportion of the low molecular weight compound in the high molecular weight compound is preferably 15% by weight or less.

The polymer compound of the present invention preferably contains the structural unit represented by the general formula (I) in a molar ratio of 20% or more, preferably,
Contains 30-90%. Further, the polymer compound of the present invention contains the structural unit represented by the general formula (II) in a molar ratio of 5% or more, preferably 10 to 70%. If the amount of the structural unit represented by the general formula (II) is too small, the solubility in an alkaline aqueous solution will be insufficient, and if it is too large, the strength of the image area will deteriorate and the sensitivity will decrease.

The polymer compound of the present invention may be a random polymer or a block polymer obtained by copolymerizing the above monomers, but it is preferable to use a random polymer.

The content of the polymer compound of the present invention is 10 to 99% by weight, preferably 50 to 95% by weight, based on the photosensitive composition.

By the way, in Japanese Unexamined Patent Publication No. 52-988, etc., the general formula (
A photocrosslinkable polymer compound containing a carboxylic acid group or a hydroxyl group in the structural unit represented by I) is described, but when this polymer compound is used, the strength of the image area may deteriorate. , which is not preferable because it causes a decrease in sensitivity.

The same publication also describes a photocrosslinkable polymer compound containing a structural unit represented by the following general formula (V).

(In the formula, R', R', R' and is inferior to the polymer compound of the present invention, and when a lithographic printing plate is prepared using this polymer compound, it is not preferable because stains will occur in the non-image areas on the printed matter.

That is, the polymer compound of the present invention has necessary and sufficient solubility in an aqueous alkaline developer by containing an appropriate hydrophilic group in the portion A in the structural unit represented by the general formula (V).

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

As photosensitizers, triplet sensitizers are preferred which have a maximum absorption that allows practically sufficient light absorption in the range of 300 nm or more.

Sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds,
Examples include benzothiazole derivatives, benzodithiol derivatives, naphthofuranone compounds, pyrylium salts, thiapyrylium salts, and the like. Specifically, Michler's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-methyl-1,3-diaza-1,9-
benz) anthrone picramide, 5-nitroacenaphthene, 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorene, 2-dibenzoylmethylene-3-methylnaphtho Thiazoline, 3,3-carbonyl-bis(7-ethyl-minocumarin), 2.4.6-)IJ phenylthiapyrylium verchlorate, 2-(p-chlorobenzoyl)naphthothiazole, 2-(5-t- Butyl-1,3
-benzodithiol-2-ylidene)-1,,3-diethylthiobarbylic acid and the like. The amount of these sensitizers added is about 1 to about 20% by weight of the total composition.
, preferably 3 to 10% by weight.

In addition to the above, a diazo resin having a negative effect can be added if necessary. Such diazo resins include 4-diazo-diphenylamine, 1-diazo-4-N,
N-dimethylaminobenzene, 1-diazo-4-N,N
-diethylaminobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, ■-diazo-2,5-jetoxy-4-benzoyl Aminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-4-N,N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1
-diazo-2,5-dimethoxy-4-p-)lylmercabutobenzene, 1-diazo-2-ethoxy-4-N,N
-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo-2,5-jethoxy-4-
Morpholinobenzene, 1-diazo-2゜5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-
Jetoxy-4-morpholinobenzene, 1-diazo-
2,5-jethoxy-4-p-)lylmercabutobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-
Benzylaminobenzene, 1-diazo-3-chloro-4
-N, N-diethylaminobenzene, 1-diazo-
3-methyl-4-pyrrolidinobenzene, 1-diazo-2
-chloro-4-N,N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3 −(
II-propoxy)-4-diazophenylamine, a-
;r A diazo monomer such as sobroboxy-4-diazodiphenylamine and a condensing agent such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, respectively, in a molar ratio of 1:1 to 1:0.5, preferably is l:0.
8 to 1:0.6, and a reaction product of a condensate obtained by condensing this in a usual manner and an anion can be mentioned. Examples of anions include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-0-
Toluenesulfonic acid, 5-sulfosalicylic acid, 2.5-
Dimethylbenzenesulfonic acid, 2,4.6-)limethylbenzenesulfonic acid, 2-nitrobenzenesulfone 13
-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid,
Examples include dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and para-toluenesulfonic acid. Among these, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2.
Alkyl aromatic sulfonic acids such as 5-dimethylbenzenesulfonic acid are preferred.

In addition, the aforementioned diazo monomer and an aldehyde or its acetal having a carboxylic acid and/or phenol (
Furthermore, if necessary, a reaction product of a condensate obtained from the above-mentioned condensing agent) and the above-mentioned anion, or JP-A-1-1024
Diazo resins described in JP-A No. 56 and JP-A-1-102457 are also preferably used in the present invention.

The amount of these diazo resins added to the total composition is generally 0.
．． 1-1.5% by weight, preferably 0.3-5% by weight.

Further, these diazo resins can also be used as an intermediate layer between the photosensitive layer and the support.

In addition to the polymer compound of the present invention, the photosensitive composition of the present invention may contain known alkali-soluble high Molecular compounds can be included. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive composition, such as hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4
．． 4'-thiobis(3-methyl-6-t-butylphenol), 2゜2'-methylenebis(4-methyl-6-
(t-butylphenol), 2-mercaptobenzimidazole, etc. are useful, and in some cases, dyes or pigments, and pH indicators as printing agents may be added for the purpose of coloring the photosensitive layer.

Typical printing agents include a combination of a photosensitive compound that releases an acid upon exposure to light and an organic dye that can form a salt.

Furthermore, phosphoric acid, phosphorous acid,
Tartaric acid, citric acid, malic acid, dipicolinic acid, polynuclear aromatic sulfonic acid and its salts, sulfosalicylic acid, etc. can be added as necessary.

Furthermore, the photosensitive composition of the present invention may contain a plasticizer and the like. As the plasticizer, phthalic acid dialkyl esters such as dibutyl phthalate and dibutyl phthalate, oligoethylene glycol alkyl esters, phosphate ester plasticizers, and the like can be used.

The photosensitive composition as described above may be used, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, N,N-dimethylformamide, N, It is coated on a support by dissolving it in a suitable solvent such as N-dimethylacetamide, dimethyl sulfoxide, ethylene dichloride, methyl lactate, ethyl lactate, water, etc. alone or in a mixed solvent of a suitable combination thereof. The coating amount is suitably in the range of about 0.1 g/m'' to about 10 g/m'', preferably 0.5 to 5 g/m'', based on the weight after drying.

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 silicon, copper, manganese, magnesium2. An alloy of aluminum and metals such as chromium, zinc, lead, bismuth, and nickel is used. 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. In addition, as described in U.S. Pat. No. 2,714,066, silicic acid is applied after graining) IJ
Aluminum plates immersed in a chromium solution are also suitable, as described in U.S. Pat. used for.

The above-mentioned anodizing treatment may be carried out 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.

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 from the surface and expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants, etc. are used.

On the other hand, 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 as the graining method. Mechanical methods include the ball polishing method, blast polishing method, and brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush.
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. 55-137
A surface roughening method that combines mechanical roughening and electrochemical roughening as described in Japanese Patent No. 993 is preferred because it provides strong adhesion of the oil-sensitive image to 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, it is necessary that no film different from aluminum derived from the etching solution components is formed on the etched surface. Examples of preferred etching agents include basic substances such as sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate; acidic substances such as sulfuric acid and persulfuric acid. , phosphoric acid, hydrochloric acid, and their salts, etc. However, salts of metals with low reionization tendency such as aluminum, such as zinc, chromium, cobalt, nickel, copper, etc., are not preferred because they form an unnecessary film on the etching surface. .

It is most preferable to use these etching agents at concentrations and temperatures so that the dissolution rate of the aluminum or alloy used is 0.3 to 40 g/ml per minute of immersion time. It doesn't matter whether it's higher or lower.

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/m.
' is preferably processed.

As the above-mentioned etching agent, it is desirable to use an aqueous base solution because of its high etching rate. In this case, since smut is generated, desmut processing 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, when a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more of these, aluminum An anodized coating can be formed on the surface of the support.

The processing conditions for anodizing cannot be determined unconditionally because they vary depending on the electrolyte used; however, for boat fishing, the electrolyte concentration is 1 to 80% by weight, the liquid temperature is 5 to 70°C, and the current density is Appropriate ranges are 0.5 to 60 A/dm', voltage 1 to 100 V, and electrolysis time 30 seconds to 50 minutes.

Among these anodizing treatments, especially British Patent No. 1.4
12,768 and U.S. Pat. No. 3,511.6.
The method of anodizing using phosphoric acid as an electrolytic bath described in No. 61 is preferred.

The aluminum plate roughened as described above and further anodized may be subjected to a hydrophilic treatment if necessary. Preferred examples thereof include US Pat. No. 2,714.066 and US Pat. Alkali metal silicates, such as aqueous sodium silicate solutions as disclosed in Japanese Patent Publication No. 461, or potassium fluorozirconate as disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. No. 4.153.
．． There is a method of treatment with polyvinylsulfonic acid as disclosed in US Pat.

Furthermore, after these treatments, aqueous resins such as polyacrylic acid, polymers and copolymers having sulfonic acid groups in their side chains, other low molecular weight compounds soluble in alkaline aqueous solutions, triethanolamine salts, and alanine compounds are removed. It is also suitable to use an undercoat.

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 alkaline developer, provides a negative relief image on the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, laser beams, and the like.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent developability when developed with an aqueous alkaline developer after coating, drying, and image exposure. Appropriate developability is obtained when developed, and appropriate developability is also obtained when developed with an aqueous alkaline developer that does not substantially destroy these organic substances.

Furthermore, when used as a printing plate, no staining occurs in non-image areas, and many good-quality printed materials can be obtained.

Therefore, it has become possible to develop negative-working planographic printing plates using an aqueous alkaline developer that is known as a developer for positive-working planographic printing plates, and can process both positive-working planographic printing plates and negative-working planographic printing plates. To avoid the trouble of adjusting the developer composition to suit each, replacing the developer composition, and preparing two types of developer compositions and development processing equipment in advance when This makes it possible to improve work efficiency,
Equipment costs, installation space, etc. are significantly improved.

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

Synthesis Example 1 126 g (1 mole) of 2,3-dimethylmaleic anhydride, 131 g (1 mole) of 6-aminocaproic acid, and 600 g of toluene were placed in a flask equipped with a stirrer and a cooling tube, and while heating to 100°C, Stir for hours. Next, a Dean-3tark water separator was attached, and the mixture was stirred for 3 hours while removing toluene reflux sewage. After the reaction was completed, the mixture was cooled and crystallized in 1.5 ml of hexane. The solid obtained by filtration and drying is further diluted with 1.5 ml of water.
Resurrected to f. By filtering and drying, 231 g of a white solid of the following compound (i) was obtained.

0 Next, 57.4 g (0.24 mole
) and thionyl chloride 29.7 g (0.25 mol
e) and stirred at room temperature for 1 hour. The mixture was further heated to 80°C and stirred for 1 hour. After the reaction was completed, it was cooled and 150 ml of ether was added. Next, a dropping funnel was attached to the flask, and while cooling the reaction mixture in an ice-water bath, 26.0 g (2-hydroxyethyl methacrylate) (0,2
mole ) and pyridine 31.6 g (0.4 mole
) was added dropwise over about 30 minutes using a dropping funnel. After dropping, stir in an ice water bath for 1 hour, and then stir for 5 hours.
The mixture was stirred for 2 hours while heating to 0°C. After the reaction was completed, the reaction mixture was cooled and put into a separating funnel together with 400 ml of ethyl acetate. The mixture was washed with water, IN hydrochloric acid, water, saturated aqueous sodium bicarbonate solution, and water in this order.

After drying this solution with sodium sulfate, the solvent was distilled off under reduced pressure to obtain 59 g of a liquid compound (ii) shown below.

Next, a 200 mj equipped with a stirrer, cooling tube, and dropping funnel.
'1-Methoxy-2-propertool 30.1 in flask
g and heated to 75° C. under a nitrogen stream. Into this flask, 22.8 g (0,065 mol) of compound (if) was added.
e), methacrylic acid 3.0 g (0,035 mo
le ), 2. A mixture of 1.15 g (0,005 mole) of dimethyl 2'-azobisisobutyrate and 30.1 g of l-methoxy-2-propatol was added dropwise through a dropping funnel over 2.5 hours. After dropping, add 7 more
After stirring at 5° C. for 3 hours, a stirring bar was added to water 11.

The precipitate was collected by filtration and dried to obtain 24 g of white solid. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 21.000 (polymer compound (a) of the present invention).

Synthesis Examples 2 to 7 Polymer compounds (b) to (g) of the present invention shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight (polystyrene standard) of these polymer compounds is 1.
It was 5.000 to 82.000.

Synthesis of a polymer compound as a comparative example According to the method described in JP-A No. 52-3055, the first
Polymer compounds (h) and (i) shown in the table were synthesized. Weight average molecular weight of this polymer compound (polystyrene standard)
were 40,000 and 23,000, respectively.

Example The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a 400 mesh water suspension of 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% HNO3, and washed with water. This was electrolytically roughened in a 1% nitric acid aqueous solution using an alternating sinusoidal waveform current under the condition of VA = 12.7 V with an anode electricity amount of 160 chrome/dm. When the roughness was measured, it was 0.6μ (Ra display).Subsequently, it was immersed in a 30% H2SO, aqueous solution and desmutted for 2 minutes at 55°C.
It was anodized for 2 minutes in a 0% H2SO aqueous solution at a current density of 2 A/dm'' to a thickness of 2.7 g/m'.

The following photosensitive liquids [A]-1~ were applied to the obtained aluminum plate.
CA:l-7 was applied using a wheeler and heated at 80℃ for 2 hours.
Dry for a minute. The dry weight was 1.5 g/m'.

The polymer compounds used in the present invention in photosensitive solutions [A]-1 to CAl-7 are shown in Table 2.

Photosensitive liquid [A] Next, as a comparative example, a photosensitive liquid [:B: l-1~ Apply [B]-2 in the same way,
Dry.

The comparative polymer compounds used in the photosensitive solutions [:B]-1 to CB]-2 are shown in Table 2.

Photosensitive liquid 1: A]-1 to [A]-7, and [B)-1 to
Each photosensitive lithographic printing plate [A] obtained using CB]-2
-1 to [:A:l-7 and [:B]-1 to CB]-2 were each image-exposed for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■, and each was applied to the following developer. After soaking for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton.

Developer: Images were obtained with the lithographic printing plates [:A]-1 to [A]-7 and [B]-1, but no images were obtained with CB]-2.

Next, each of the printing plates thus obtained was mounted on a Heidelberg GTO type printing machine and printed on high-quality paper using commercially available ink.

At this time, stains occurring on the paper in non-image areas were visually determined. (O: No stain, ×: Stain) The results are shown in Table 2.

Lithographic printing plate [:A]-1 using the polymer compound of the present invention
~I''A: All of l-7 did not cause staining, but lithographic printing plate 1''B]-1 using a comparative polymer compound did stain.

No. table hand Continued Supplementary Positive book

Claims (1)

[Claims] A photosensitive composition containing a photocrosslinkable polymer compound, wherein the photocrosslinkable polymer compound has a structural unit represented by the following general formula (I) and a structural unit represented by the general formula (II). A photosensitive composition comprising a structural unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(II) (In the formula, R^1 and R^6 each represent a hydrogen atom, a methyl group, or a halogen group, and R^2 represents a divalent carbonized represents a hydrogen group, R^3 represents a divalent hydrocarbon group which may have an ether, ester or amide bond, R^4 and R^5
each represents a hydrogen atom, an alkyl group of C_1 to C_4, or a halogen group, R^4 and R^5 may be taken together to form a 5- or 6-membered ring, and X is -O- or -NH -, Y represents an ether, ester or amide bond, and Z represents a single bond or a divalent linking group consisting of two or more atoms of C, H, N and O. )