JP3078152B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition suitable for the production of lithographic printing plates, proofs for multicolor printing, IC circuits, and photoresists. More specifically, the present invention relates to a photosensitive composition containing a polymer that decomposes by light to generate free radicals or acids. More specifically, the present invention relates to a photosensitive composition containing a polymer having a sulfonimide group as a photodegradable compound.

[0002]

BACKGROUND OF THE INVENTION Compounds that decompose on exposure to light to form free radicals or acids are well known in the graphic arts, photoresist, coating and dental fields. They are photoinitiators in the photopolymerizable composition, and photoacid generation in reactions catalyzed by light-generated acids, such as polymerization, crosslinking, deprotection, elimination, and decomposition reactions. Widely used as an agent.
Compounds that generate an acid by being decomposed by light are widely used as a dissolution accelerator in the field of photoresists and PS plates. Well-known examples of compounds that decompose upon exposure to generate free radicals or acids include organic halogen compounds. Organic halogen compounds are photolyzed to give halogen radicals such as chlorine radicals and bromine radicals. These halogen radicals are good hydrogen abstracting agents and generate acids in the presence of hydrogen donors. Further, a halogen radical is a good polymerization initiator, and a polymerization reaction occurs when a compound having a polymerizable double bond is allowed to coexist. For their application to radical photographic and photopolymerization processes, see J. Kosar,
"Light Sensitive Systems" J. Willy & Sons (New
York 1965) p180-181 and p361-3
70.

Compounds which generate halogen radicals by the action of light include carbon tetrabromide, iodoform, tribromoacetophenone and the like, as well as trichloromethyl-S-
Triazine compounds have been widely used. Examples of trichloromethyl-S-triazine compounds and examples of the use thereof as a photopolymerization initiator or a photoacid generator include compounds having an aminophenyl group as described in German Patent Specification DE3726001C2 and methods of using the same. European Patent Specifications EP0519298 and EP51
Compounds having a sulfonic ester group as described in No. 9299 and methods of using the same can be mentioned. Also, European Patent Specification EP441524A
Describe a polymer having a trichloromethyl-S-triazine skeleton. Other trichloromethyl-
Examples of S-triazine compounds include Chemical Review 1993, Vol. 93, p.
Compounds such as those described in the text on page 48 and in the references can be mentioned. Other examples of compounds that decompose upon exposure to produce free radicals or acids include onium salts such as iodonium salts, sulfonium salts and diazonium salts. Examples of these compounds and examples of their use include the following patents. U.S. Pat. No. 4,837,124 discloses a positive photoresist composition using a diphenyliodonium salt as an acid generator.
EP 102450B discloses a positive photoresist composition using a triphenylsulfonium salt as an acid generator. Also, European Patent No. 420
Nos. 827A and 425891A disclose negative photoresist compositions using a diaryliodonium salt or a triarylsulfonium salt as an acid generator. No. 4,985, U.S. Pat.
No. 332 discloses a positive photoresist composition using a diazonium salt as an acid generator.

Other examples of compounds which decompose on exposure to produce free radicals or acids include European Patent No. 5
Disulfone compounds as described in JP 20265A or disulfone polymers described in JP 363198A or EP 510
1-sulfonyl-2-pyridone compounds described in JP-A-440A and JP-A-510443A, or EP-A-510441A and EP-A-5104104
And the sulfonic acid ester compounds described in JP-A-46A. No. 5,002,853.
And sulfonyl imide ester-based polymers as described in the specification. Other examples of the compound that decomposes upon exposure to generate an acid include a quinonediazide compound. Examples of the quinone diazide compound include “Quinone Diazide” by VVErshov et al.
s "ELSEVIER SCIENTIFIC PUBLISHING COMPANY (19
81). As is well known, naphthoquinonediazide generates a carboxylic acid upon exposure to light, which acts as a dissolution accelerator during alkaline development. Widely used in such as. These conventional photodegradable compounds or polymers have been widely used as acid generators, radical generators or as dissolution accelerators. However, these compounds are toxic, explosive and other safety, thermal stability,
It was not always satisfactory in terms of manufacturing suitability. Conventionally, in the production of ordinary lithographic printing plates, a step of post-exposure development processing has been required. However, this development process usually has a problem that a development processor is required, the hands are stained when handling the developing solution, and the processing of the developing waste solution is required.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition containing a novel photodegradable polymer which is excellent in safety, heat stability and production suitability. Another object of the present invention is to provide a photosensitive composition that can produce a printing plate that can be used for printing without going through a post-exposure development step.

[0006]

Means for Solving the Problems The present inventors have conducted various studies in order to achieve the above object, and as a result, have reached the present invention. The present invention provides a photosensitive composition containing a polymer having at least one sulfonimide group represented by the following general formula (1). ^{_{-L -SO 2 -NR 2 -SO 2 -R}} 1 (1) wherein R ¹ and R ² are each independently an aromatic group, substituted aromatic group, an alkyl group or a substituted alkyl group. L represents a linking group for linking a sulfonimide group to a polymer moiety. The terms “polymer moiety” and “polymer” as used herein include, for example, 10, 100, 10
A macromolecule having a molecular weight in the range of about thousands to about millions, derived from the binding of many small molecules, such as 00 or more. Small molecules that associate with one another are commonly referred to as "monomers" or "prepolymers" and the reaction by which they associate is commonly referred to as "polymerization." Polymers are structured using repeating units of the appropriate structure, which are often
4 is a structural formula of a monomer or prepolymer starting material.
For more information on polymer chemistry, reactions, monomers, properties, and nomenclature, see Odian
an), Principles of Polymerization, 2nd edition, J. Wailey & Sun (New York: 1981)
Year) and the Encyclopedia of Polymer Science Industry
Polymer Science and Engineering), J. Wailey & Sun (New York: 1988). The term "polymer" as used herein refers to a homopolymer (ie, a polymer in which all monomer units are the same),
And copolymers (ie, polymers in which two or more monomer units are present).

In the compound represented by the general formula (I),
When either R ¹ or R ² represents an aromatic group or a substituted aromatic group, the aromatic group includes a carbocyclic aromatic group and a heterocyclic aromatic group. The carbocyclic aromatic group has 6 carbon atoms
To 19 are used. Preferably a phenyl group,
Those having one to four benzene rings such as a naphthyl group, an acetracenyl group and a pyrenyl group are preferred. Further, the heterocyclic aromatic group has 3 to 20 carbon atoms and 1 to 1 heteroatoms.
5 are used. Among them, pyridyl group,
Particularly preferred are a furyl group, a quinolyl group in which a benzene ring is fused, a benzofuryl group, a thioxanthone group, and a carbazole group. When either R ¹ or R ² represents an alkyl group or a substituted alkyl group, those having 1 to 25 carbon atoms are used as the alkyl group, and in particular, methyl, ethyl, isopropyl, t A straight-chain or branched alkyl group having 1 to 8 carbon atoms such as -butyl group is particularly preferred.

When either R ¹ or R ² is a substituted aromatic group or a substituted alkyl group, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group, a fluorine atom, a chlorine atom, A halogen atom such as a bromine atom, an alkoxycarbonyl group having 2 to 15 carbon atoms or an aryloxycarbonyl group having 2 to 15 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butyloxycarbonyl group, a p-chlorophenyloxycarbonyl group; a hydroxyl group; Acyloxy groups such as benzoyloxy and p-diphenylaminobenzoyloxy; carbonate groups such as t-butyloxycarbonyloxy group; ether groups such as t-butyloxycarbonylmethyloxy group and 2-pyranyloxy group; amino groups and dimethylamino Group, diphenylamido A substituted or unsubstituted amino group such as a thio group, a morpholino group, or an acetylamino group; a methylthio group,
Thioether groups such as phenylthio group; alkenyl groups such as vinyl group and styryl group; nitro group; cyano group; acyl groups such as formyl group, acetyl group and benzoyl group; aryl groups such as phenyl group and naphthyl group; Such heteroaromatic groups; and the like. When either R ¹ or R ² is a substituted aromatic group, an alkyl group such as a methyl group or an ethyl group can be used as the substituent other than those described above.

L is a linking group for linking the sulfonimide group to the polymer moiety, and may be formed by a single group or a combination of a plurality of groups. It may be a single bond. Suitable groups for this linking group include, for example, substituted and unsubstituted alkylene groups having up to 20 carbon atoms, such as methylene and ethylene, and optionally substituted alkylene groups, phenylene, up to 20 carbon atoms such as naphthylene. arylene group, an ester group (-COO -), amide group (-CONH-), carbamate group (-NHCO ₂ -), urea group (-NHCONH-), an ether group (-O-), an amino group (-NH -), thioether group (-S-), sulfonamide group (-SO ₂ NH -), an alkylene group having up to 10 carbon atoms such as vinyl group, optionally substituted with up to 20 carbon atoms Good divalent heteroaromatic groups, and combinations thereof, are included. Of these, preferred as the group directly bonded to the sulfonimide group are an alkylene group which may be substituted and an arylene group which may be substituted, from the viewpoint of ease of synthesis. Further, when R ¹ is an alkyl group or a substituted alkyl group, L 1
Among the groups included in the above, an arylene group which may be substituted is particularly preferable as the group directly bonding to the sulfonimide group. Typical -L- group combinations are shown below. Here, X is a sulfonimide group, that is, —SO ₂ NR ¹ SO ₂ R ¹
Represents

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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In many cases, L is selected to contain a reactive or polymerizable group that is useful in a polymerization reaction to prepare a polymer containing a sulfonimide group moiety. Typical reactive groups contained in L and useful for polymerization reactions include hydroxyl; isocyanates; amines; carboxylic acids; acrylates, methacrylates, vinyl esters,
Vinyl monomers such as acrylamide, methacrylamide, and styrene; vinyl esters; and cyclic ethers. In other cases, L is selected to include a reactive group capable of binding a functional group that is bound to a preformed polymer. Examples of such reactive groups include, but are not limited to, isocyanate; hydroxyl; amine; carboxyl; acid anhydride;

It is reasonable to conclude that almost all common polymers can be modified to contain a sulfonimide group moiety by attaching to or incorporating into the main chain. Examples of common polymers include polyamide, polyester, polyurethane, polysiloxane, phenolic resin, poly (arylmethylene), polystyrene, poly (acrylate), poly (acrylic acid), polyacrylamide, polyacrylonitrile, polyethylene , Polybutadiene, polyvinyl ester, polyvinyl alcohol, polyvinyl acetal, polyvinyl ether, polyvinyl pyrrolidone, polyvinyl pyridine, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyethylene glycol, polypropylene glycol, polyethylene imine, epoxy resin, phenoxy resin, polytetrahydrofuran, polycaprolactone , Poly (styrenesulfonic acid), gelatin, alkylcellulose, hydro Shi alkyl cellulose, carboxymethyl cellulose, starch, and polysaccharides include, but are not limited to. The molecular weight can be in the thousands to millions.

One method for preparing a polymer containing a sulfonimide group of the present invention (hereinafter also referred to as a “sulfonimide polymer”) includes a sulfonimide having a reactive group and a functional group which binds to the reactive group of the sulfonimide. A method of reacting with a polymer having a group can be given. An example of such a reaction is an addition reaction between an isocyanate-substituted sulfonimide and a polymer having a group that reacts with the isocyanate group. This isocyanate-substituted sulfonimide can be obtained from its corresponding amine derivative in U.S. Pat. U.Von Gizycki, Angew. Che
m. Int. Ed. Eng., 1971, 10, 403. Typical polymers that bind to this isocyanate group include polyvinyl alcohol, poly (2-hydroxyethyl) methacrylate, polyvinyl formal, polyvinyl butyral, polycaprolactone, polyethylene oxide, polyol, polytetrahydrofuran, polyethylene adipate, hydroxy-terminated polybutadiene,
Polypropylene glycol, and various hydroxy-terminated and amino-terminated polysiloxanes are included. Isocyanate addition reaction, for example, toluene, pyridine,
The reaction can be performed in the presence of benzene, xylene, dioxane, tetrahydrofuran, and the like, and a mixed solvent thereof. The reaction time and temperature for this reaction depend on the particular compound and catalyst used in the reaction. Generally, about 2
Conditions of 5 to 150 ° C. for 1 to 72 hours are sufficient for the reaction. Preferably, the reaction is carried out at room temperature for 3-72.
Done for hours. A preferred catalyst is di-n-butyltin dilaurate. However, other catalysts may be used.

Another method of preparing a polymer containing a sulfonimide group moiety from a preformed polymer is to combine a hydroxyl- or amino-substituted sulfonimide with a polymer having a group that reacts with a hydroxyl or amino group. To react. Examples of such groups include, but are not limited to, isocyanates, epoxies, acid anhydrides, oxazolinones and chloric acid. Typical polymers containing these groups include 2-isocyanate ethyl methacrylate copolymer, isocyanate terminated oligomers of polyol and polyester, styrene-maleic anhydride copolymer, vinyl ether-maleic anhydride copolymer, glycidyl methacrylate copolymer, epoxy-modified novolak Resins and vinyl oxazolinone copolymers. A group of polymers particularly suitable for the present invention are structurally diverse, easy to synthesize, have good physical properties,
And acrylic acid polymers and acrylamide polymers are mentioned because they provide good performance.
Although they are prepared as described above, other suitable methods that may be used to prepare these materials include sulfonimides having acrylate, methacrylate, acrylamide, methacrylamide, or styrene monomer moieties attached. , Free radical polymerization. Representative examples of the sulfonimide compounds substituted with these monomers are shown below.

[0019]

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[0020]

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[0021]

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[0022]

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Comonomers useful for the copolymerization reaction with the sulfonimide-substituted monomers include acrylic acid and methacrylic acid; acrylates and methacrylates such as methyl, ethyl, butyl, octyl, 2-dimethylaminoethyl, -Methoxyethyl, 2-hydroxyethyl, 2-chloroethyl, benzyl, glycidyl, 2-cyanoethyl, 2-isocyanatoethyl, tetrahydrofurfuryl); acrylamide and its derivatives (for example, N-methylolacrylamide, N-isobutoxymethylacrylamide, And methacrylamide); vinyl ethers such as styrene, maleic anhydride, 4-vinylpyridine, 2-methacryloyloxyethane-1-sulfonic acid and salts thereof, acrylonitrile and ethyl vinyl ether. Ether, but it is included without limitation. Other examples of acrylic and acrylamide monomers can be found in the Encyclopedia of Polymer Science.
of Polymer Science), 2nd edition, Volume 1, 182, 2
04, 237, 242, and 243.

Another group of useful polymers that are easy to synthesize and versatile include polyurethanes, usually formed from diols, diisocyanates, and chain extenders. Sulfonimide derivatives having dihydroxyl or diisocyanate groups are particularly useful reactants. This dihydroxyl derivative is used directly or converted into a diisocyanate prepolymer by reaction with tolylene-2,4-diisocyanate. Other diols, such as hydroxyl terminated linear aliphatic polyesters and aliphatic polyethers, and other polycyclic diisocyanates, such as aromatic, aliphatic, cycloaliphatic or polycyclic, are used in combination. Such versatility in selecting reactants allows a wide range of molecular weights and physical properties. The technology, chemistry, basic structure, and synthetic route for polyurethane elastomers can be found in C. Hepburn, Polyurethane Elastomers, Applied Chemistry Publishing (Ap.
plied Science Publishers) (New York: 1982)
Year); and the Encyclopedia of Polymer Chemistry, 2nd edition, 13th edition
Volumes, pages 243-303. Examples of suitable dihydroxyl-substituted sulfonimides that can be used in preparing polyurethanes are provided below.

[0025]

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However, it should not be considered that the preferred dihydroxyl substituted sulfonimides used in the present invention are limited to the compounds in the above table. The amount of sulfonimide groups contained in the polymer of the present invention ^{_{(-SO 2 NR 2 SO 2 R}} 1) may range 0.01 to 99% by weight. However, it is practically used in the range of 0.1% to 98%. The molecular weight of the polymers of the present invention is from about 1,000 to about 1,000,000.
00 or more. A preferred molecular weight range is from about 5,000 to about 1,000,000.

The production example of the polymer having a sulfonimide group according to the present invention is shown below. Synthesis Example of Monomer Synthesis of Compound No. 1 in Table 1 N-methylstyrenesulfonamide (88.8 g), triethylamine (109.3 g), dimethylaminopyridine (5.5 g) and acetonitrile (200 ml) were placed in a 1-liter three-necked flask. The flask was ice-cooled and, with stirring, 119.2 g of benzenesulfonyl chloride dissolved in 200 ml of acetonitrile was added dropwise over 1 hour. Room temperature after dropping
After stirring for an hour, the mixture was left overnight. The reaction solution is water 800
The mixture was poured into 500 ml, extracted with 500 ml of ethyl acetate, dried over magnesium sulfate and concentrated. The concentrate was purified by silica gel chromatography (using hexane / ethyl acetate = 3/1 (volume ratio)) and then recrystallized from 300 ml of isopropyl alcohol. 80.3 g of white crystals having a melting point of 58.5-60 ° C. were obtained. Absorption spectrum (in THF) λmax 265 nm ε: 2.0 × 10 ⁴ Elemental analysis: C: 53.21% H: 4.53% N: 4.17%

Synthesis Example 1 of Polymer Having Sulfonimide Group 16.87 g of the compound No. 1 in Table 1 and 33.74 g of dimethylformamide were placed in a 100 ml three-necked flask, and kept at 65 ° C. while stirring under a nitrogen stream. Was. 12.4 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and stirring was continued. Two hours later, 2,2'-azobis (2,4
-Dimethylvaleronitrile) was added in an amount of 31.1 mg. After stirring for 4 hours, the mixture was cooled to room temperature, and the reaction solution was poured into 500 ml of methanol. The precipitated solid (polymer) was collected by filtration and dried. The weight average molecular weight of this polymer measured by GPC was 32,000. (Yield 9.72 g) Synthesis Example 2 of Polymer Having Sulfonimide Group 15.18 g of the compound No. 1 in Table 1, 0.71 g of glycidyl methacrylate and 31.78 g of dimethylformamide were added in 1 part.
The mixture was placed in a 00 ml three-necked flask and kept at 65 ° C. while stirring under a nitrogen stream. 12.4 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and stirring was continued. Two hours later, 31.1 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was further added. After stirring for 4 hours,
After cooling to room temperature, the reaction solution was poured into 500 ml of methanol. The precipitated solid (polymer) was collected by filtration and dried. G
The weight average molecular weight of this polymer measured by PC was 4.
It was 630,000. (Yield 9.9g)

The polymer containing a sulfonimide group according to the present invention is efficiently decomposed to generate a radical or an acid when irradiated with an actinic ray having a wavelength within the range of about 200 nm to 500 nm. Accordingly, the polymer according to the present invention comprises a photosensitive composition containing a photodegradable compound as an essential component, a photosensitive composition containing a compound capable of generating a radical upon irradiation with actinic light, and an actinic ray. Can be usefully used as a photodecomposable compound, a photoradical generator and a photoacid generator of a photosensitive composition containing a compound capable of generating an acid as an essential component. Furthermore, the polymer according to the present invention has excellent characteristics in terms of safety, suitability for production, and thermal stability as compared with conventionally known photodegradable compounds. Accordingly, by using the polymer of the present invention, a photosensitive composition that is safe and has good thermal stability can be produced. The photodegradable polymer according to the present invention can be used in place of a photodegradable compound, ie, naphthoquinonediazide, conventionally used in a positive printing plate or a positive photoresist. Naphthoquinonediazides are, as is well known, highly explosive compounds. Therefore, great care must be taken with this production. Compared with naphthoquinonediazides, the photodegradable compound of the present invention has a low explosive property and can be produced safely.

When the sulfonimide polymer of the present invention is used in the production of a positive printing plate or a positive photoresist instead of naphthoquinonediazide, only the polymer of the present invention may be used, but various desired properties are obtained. Therefore, it may be used by mixing with another polymer. As such other polymer, any polymer having a molecular weight of 1,000 or more is used, and particularly, a polymer which is insoluble in water but soluble or at least swellable in an aqueous alkaline solution is preferable. Preferred examples of such polymers include, for example, novolak resins, hydrogenated novolak resins,
Acetone-pyrogallol resin, polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, Examples thereof include, but are not limited to, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof. Particularly preferred alkali-soluble resins are novolak resins and polyhydroxystyrene. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2- Alkoxyphenols such as methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropylphenol Bis-alkylphenols etc., m
-Hydroxyaromatic compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more. It is not limited.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, such as chloroacetaldehyde dieter acetal, can be used, and among these, formaldehyde is preferred. These aldehydes are
They are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used. The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred is the range 2,000-20,000.

Other preferred binders include p-
Hydroxystyrene and its alkyl derivatives, for example, a homopolymer or copolymer of 3-methylhydroxystyrene, and other polyvinylphenols, for example, a homopolymer or copolymer of 3-hydroxystyrene, or acrylic acid and a phenolic hydroxyl group And an ester or amide with an aromatic compound. Styrene, methacrylic acid, methacrylic acid esters, acrylic acid, acrylic acid esters and the like can be used as comonomers in the copolymer. The preparation of copolymers of the type described above using silicon-containing vinyl monomers, for example vinyltrimethylsilane, results in mixtures with increased resistance to plasma etching. The transparency of these binders is generally high in the areas of interest, so that pattern formation can be improved. The same effect can be obtained by using a maleimide homopolymer or copolymer. Styrene, substituted styrene, vinyl ethers, vinyl esters, vinyl silyl compounds or (meth) acrylates can also be used as comonomers. Finally, the styrene copolymer is
It is also possible to use with comonomers which increase the solubility in aqueous alkaline solutions. These include, for example, maleic anhydride, maleic acid half ester, and the like. These binders can be mixed. But,
Preferred are binders comprising one of the above types.

In addition, if desired, in addition to dyes, pigments, wetting agents and leveling agents, polyglycols, cellulose ethers, such as ethylcellulose, are added to the photodegradable mixture according to the invention to provide flexibility, adhesion and gloss. And other characteristics can be improved. When the sulfonimide polymer of the present invention is used in combination with a binder, the amount of the sulfonimide polymer is generally 1 to 9 based on the total weight of the binder and the sulfonimide polymer.
It is used in an amount of 9.99% by weight, particularly preferably 5 to 99.9% by weight. Further, the photodegradable compound of the present invention can be used as a photoacid generator, such as C—O—C— or C—O—, which can be cleaved by an acid.
It can be used in combination with a compound having a Si-bond. C—O—C— or C—O— cleavable by an acid
As compounds having a Si-bond, the following types of compounds have been found to be particularly effective.

A) containing at least one orthocarboxylic acid ester and / or carboxylic acid amide acetal group, whose compounds can be polymerizable and the above-mentioned groups being used as crosslinking elements in the main chain or as side-substituted B) oligomeric or polymeric compounds containing repeating acetal and / or ketal groups in the main chain, c) compounds containing at least one enol ether or N-acylaminocarbonate group, d) cyclic acetal or ketal of β-ketoester or β-ketoamide, e) a compound containing a silyl ether group, f) a compound containing a silyl enol ether group, g) an aldehyde or ketone component is added to the developer in an amount of 0.1 to 0.1%. Monoacetal or monoketal with solubility of 100 g / l H) tertiary alcohol-based ethers, and i) tertiary aryl or benzyl alcohol carboxylic esters and carbonates.

Compounds of the type (a) which can be cleaved by acid as components of the radiation-sensitive mixture are described in German Patents 2,610,842A and 2,928,636A. Mixtures containing compounds of type (b) are described in German Patents 2,306,248C and 2,71
No. 8,254C. Compounds of class (c) are described in EP 0,006,626A and EP 0,006,627A. Compounds of type (d) are described in EP 0,202,196A and compounds used as type (e) are described in German Patents 3,544,165A and 3,601,264A. Compounds of type (f) are described in German Patents 3,730,785A and 3,730,783A, and compounds of type (g) are described in German Patent 3,730,783A. Compounds of type (h) are described, for example, in U.S. Pat. No. 4,603,101; compounds of type (i) are described, for example, in U.S. Pat.
491,628 and JMFrechet et al., J. Imaging Sci. 30,
59-64 (1986). It is also possible to use mixtures of the above-mentioned substances which can be cleaved by acids. Among the above-mentioned compounds (a) to (i), particularly preferred are substances belonging to types (a), (b), (g) and (i). In class (b), particular attention should be given to polymerizable acetals, and among the class (g) substances which can be cleaved by acids, in particular the aldehyde or ketone component is above 150 ° C., preferably Attention should be paid to compounds having a boiling point above 200 ° C.

Other preferred acid cleavable substances include organic polymers having a C—O—C— or C—O—Si— bond. Examples thereof include acid-decomposable ethers, esters, carbonates, acetals, ketals, and organic polymers containing silyl ether groups. Specific examples of these organic polymers are described in EP 0520265A, U.S. Pat.No. 4,985,332, West German Patent 271,825.
Nos. 4, 3601,264 and U.S. Pat. No. 4,931,379. When the sulfonimide polymer of the present invention is used in combination with an acid-cleavable compound, at least one polymer that is insoluble in water but soluble or at least swellable in an aqueous alkaline solution as described above is further used. They may be used in combination. When the sulfonimide polymer of the present invention is used in combination with an acid-cleavable compound, the amount of sulfonimide polymer is based on the total weight of the sulfonimide polymer, the acid-cleavable compound, and the alkali-soluble or swellable polymer. On the other hand, it is 0.1 to 25% by weight, preferably 1 to 10% by weight. The amount of the compound that can be cleaved by an acid is 1 to 99.9% by weight, preferably 5 to 99% by weight. The amount of the alkali-soluble or swellable polymer is 0 to 98% by weight, preferably 0 to 95% by weight.

Further, the negative photosensitive composition can be prepared by combining the sulfonimide polymer of the present invention with a compound having at least two acid crosslinkable groups in the same molecule. As the compound having an acid crosslinkable group, British Patent No. 2082
No. 339, resole resins as disclosed in EP 0 212 482 A, aromatic compounds substituted with alkoxymethyl or oxiranylmethyl groups as disclosed in EP 0 212 482 A and EP 0 133 216 A, West German Patent 3634371 A
And melamine-formalin condensate or urea-formalin condensate, which are monomers or oligomers described in the specifications of JP-A Nos. 3711264 and 3711264. Particularly preferred examples of the compound having an acid crosslinkable group are the compounds used in EP 0212482A. Preferred typical examples of the compound having an acid crosslinkable group are compounds in which two or more hydroxymethyl groups, acetoxymethyl groups, methoxymethyl groups, or the like are substituted on the aromatic ring or the hetero ring. Of these, melamine-formaldehyde resins having at least two or more N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups are particularly useful. When the sulfonimide polymer of the present invention is used in combination with a compound having an acid-crosslinkable group, at least one which is insoluble in water as described above but is soluble or at least swellable in an aqueous alkali solution. Two polymers may be used in combination. When the sulfonimide polymer of the present invention is used in combination with an acid-crosslinkable compound, the amount of the sulfonimide polymer is based on the total weight of the sulfonimide polymer, the acid-crosslinkable compound, and the alkali-soluble or swellable polymer. On the other hand, 0.1
-25% by weight, preferably 1-10% by weight. The amount of the compound which can be crosslinked with an acid is 0.1 to 99.9% by weight, preferably 1 to 50% by weight. The amount of the alkali-soluble or swellable polymer is 0 to 98% by weight, preferably 0 to 95%.
% By weight.

The sulfonimide polymer of the present invention can be used in combination with a polymerizable ethylenic compound as a photoradical generator. The polymerizable compound having an ethylenically unsaturated bond used in the present invention is a compound having at least one, more preferably two or more ethylenically unsaturated bonds in its chemical structure. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of the monomer and its copolymer include an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Specific examples of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate as an acrylate ester,
Triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, Methylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate Acrylate, dipentaerythritol Tiger acrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3 -Methacryloxy-2- Mud propoxy) phenyl] dimethyl methane, bis - [p- (acryloxyethoxy) phenyl] dimethylmethane. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis -Methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. These are used in an amount of 5% by weight or more, preferably 10% by weight to 99.5% by weight, based on the entire photosensitive composition.

The combination of the sulfonimide polymer of the present invention and a polymerizable compound having an ethylenically unsaturated bond may be used by further adding a binder. As the binder, any polymer can be used as long as it is a polymer having compatibility with the photopolymerizable ethylenically unsaturated compound. Desirably, water or weakly alkaline water-soluble or swellable organic high molecular polymers should be selected to enable water development or weakly alkaline water development. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such an organic high molecular polymer include polymers such as the above-mentioned novolak resin which are insoluble in water but soluble or at least swellable in an aqueous alkali solution. Other organic high molecular weight polymers include addition polymers having a carboxylic acid in the side chain, for example,
-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836,
JP-A-59-71048, each of which discloses a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid. There are copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally Other addition-polymerizable vinyl monomers)
Copolymers are preferred. These organic high-molecular polymers can be mixed in any amount in the whole composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like.

If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent the polymerization from being inhibited by oxygen so as to be unevenly distributed on the surface of the photosensitive layer. The amount of the higher fatty acid derivative added is about the total amount of the photosensitive composition.
0.5% to about 10% by weight is preferred. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of dye and pigment added is about 0.5% by weight of the total composition.
About 5% by weight is preferred. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film. The sulfonimide polymer represented by the general formula (I) in the present invention can be used in a photosensitive resist-forming composition for producing a lithographic printing plate, an IC circuit, a photomask, or the like without being exposed to light immediately without being developed by exposure. This is particularly useful when giving a performance of giving a visible contrast between the printed portion and the printed portion (hereinafter referred to as a printout capability).
A photosensitive resist composition having such a printout ability can obtain a visible image only by exposure under a yellow safety lamp in an exposure operation, for example, in the process of simultaneously exposing many printing plates, for example, the work is interrupted. It is possible to know whether or not the plate given to the platemaker has been exposed, for example, when the plate has been exposed. Similarly, when a large plate is repeatedly exposed to light, for example, in a so-called printing plate printing method for making a lithographic printing plate, an operator should immediately check which part has been exposed. Can be.

The composition used for imparting such printout ability (hereinafter referred to as a printout composition) is discolored by a free radical generator or an acid generator and a free radical or an acid generator. According to the present invention, the sulfonimide polymer represented by the general formula (I) is used as the free radical generator or the acid generator. As the color changing agent used in the present invention, a color changing agent changes from a colorless state to a colored state by reacting with a free radical or an acid generated from the sulfonimide polymer of the present invention, and a color changing agent having an inherent color changes. There are two types, one that removes or decolorizes. Representative examples of the color changing agent belonging to the former type include arylamines. Arylamines suitable for this purpose include simple arylamines such as primary and secondary aromatic amines, as well as so-called leuco dyes, examples of which include: Diphenylamine, p, p'-tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-phenylenediamine, p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriphenylmethane P, p'-tetramethyldiaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p', p"
-Triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-4-anilinonaphthylmethane.

Further, it originally has a unique color, and this color changes due to the action of the acid generated from the sulfonimide polymer,
As the discoloring agent that discolors, various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminonaphthoquinone, and azomethine are effectively used. Examples of these include the following.
Brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, Methanil yellow,
Thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone,
2,7-dichlorofluorescein, paramethyl red,
Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Phenacetaline, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Pink # 312 [ Orient Chemical Co., Ltd.], Oil Red 5B (Orient Chemical Co., Ltd.), Oil Scarlet # 308 (Orient Chemical Co., Ltd.), Oil Red OG (Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiro Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6
G, fast acid violet P, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p
-Diethylaminophenylimino naphthoquinone, 2-carbostarylamino-4-p-dihydroxyethyl-
Amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5 -Pyrazolone, 1- [beta] -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

The ratio of the above-mentioned discoloring agent to the sulfonimide polymer represented by the general formula (I) is such that the sulfonimide polymer represented by the general formula (I) is about 0.1 part by weight based on 1 part by weight of the discoloring agent. The range is from 01 parts to about 100 parts by weight, more preferably 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. On the other hand, as described above, the photosensitive resist-forming composition to be provided with the printout ability by the printout composition according to the present invention forms various printing plates such as planographic printing plates, IC circuits, and photomasks. It is useful when used together with various photosensitive materials used for the above-described processing. Examples of the photosensitive material used together with such a printout composition include a diazo resin represented by a condensate of p-diazodiphenylamine and paraformaldehyde, a quinonediazide compound represented by o-naphthoquinonediazide, and polyvinyl cinnamate. Mate resin,
Photocrosslinkable resins represented by dimethylmaleimide group-containing resins, photopolymerizable compositions comprising an addition polymerizable unsaturated compound represented by pentaerythritol tetraacrylate and a photopolymerization initiator, and the like. it can. The printout composition comprising the sulfonimide polymer according to the present invention and a color-changing agent, in addition to the above-described photosensitive material,
It can be used with various binders. As such a binder, those similar to those used in combination with a photopolymerizable ethylenically unsaturated compound can be used. When such a photosensitive composition contains a printout composition comprising the sulfonimide polymer and a color-changing agent, the amount of the color-changing agent is 0.001% by weight based on the total weight of the photosensitive composition. 20% by weight, preferably 0.01% to 10% by weight, and the amount of photodegradable polymer ranges from 0.0001% to 10% by weight, preferably 0.001% to 2% by weight.

In the photosensitive film coated with the sulfonimide polymer of the present invention, the properties of the film surface are greatly changed from lipophilicity to hydrophilicity by exposure or heating. Therefore, by using the sulfonimide polymer according to the present invention, it is possible to produce a printing plate that can be printed without performing development processing. When the sulfonimide polymer of the present invention is used for the production of a printing plate that does not require a development treatment, the sulfonimide polymer may have any structure described in the general formula. The skeleton contains a functional group which can be cured or cross-linked by heat or light. Note that the terms curing and cross-linking used herein are synonymous and are hereinafter referred to as curing. The functional group that can be cured by heat or light refers to a functional group that causes a resin to undergo a curing reaction by at least one of heat and light. Specific examples of the photocurable functional group include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha, 1977), Takahiro Tsunoda, "New Photosensitive Resin" (publishing department of Printing Society, 1981), GE Green and B.
P. Strak, J. Macro. Sci. Reas. Macro. Chem. C21 (2)
187-273 (1981-82), CG Rattey,
`` Photopolymirization of Surface Coatings '' (A. W
iley Inter Science Pub., 1982), and the like, functional groups used in conventionally known photosensitive resins and the like are used as the photocurable resin.

Further, the “thermosetting functional group” in the present invention
For example, Takeshi Endo, "Precision of Thermosetting Polymers
(CCM Co., Ltd., 1985), Yuji Harasaki
New Binder Technology Handbook ”, Chapter II-I (General Technology Center)
ー, 1985), Takatsu Otsu "Synthesis of acrylic resin
Design and New Application Development ”(Chubu Management Development Center Publishing Department, 1
985), Eizo Omori “Functional acrylic resin” (te
Functional groups described in reviews such as Kunosystem, 1985)
Can be used. For example, -COOH group, -PO_ThreeH_TwoGroup,
−SO_TwoH group, -OH group, -SH group, -NH_TwoGroup, -NHR _AGroup [R
_ARepresents a hydrocarbon group, for example, an alkyl having 1 to 8 carbon atoms.
And a radical. ], A cyclic acid anhydride containing group,
-N = C = O group, blocked isocyanate group, active
Tylene compounds (acetylacetone, acetoacetate
, Malonic diesters, malondinitrile, etc.), rings
N-atom-containing compounds (eg imidazole, piperazi
, Morpholine, etc.), and -CONHCH_TwoOR_B
[R _BRepresents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (specifically,
Typically R_AThe same content as the alkyl group of the above). ],-
Silane coupling group containing at least one OR group
[For example, -Si (OR)_Three, -Si (OR)_Two(R), -Si (OR) (R)_TwoIn
And R represents a hydrocarbon group. ], -OR group at least
Titanate coupling group containing one, epoxy
Group, glycidyl group, acrylate group, methacrylate
Group, acrylamide group, allyl group, vinyl group
Examples include a polymerizable double bond group.

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Things. Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, and a cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic anhydride ring, 2,3-bicyclo [2,2
2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Is also good. Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. For example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for example, as an alkoxy group, Methoxy group, ethoxy group, etc.) may be substituted.

The above-mentioned blocked isocyanate group is a functional group which is decomposed by heat to form an isocyanate group in an adduct with a compound. For example, as an active hydrogen compound, 2,2,2-trifluoro Ethanol, 2,2
2,2 ', 2', 2'-hexafluoroisopropyl alcohol phenols (phenol, chlorophenol,
Examples include cyanophenol, cresol, and methoxyphenol. When the photosensitive composition containing the sulfonimide polymer of the present invention is used for production of a printing plate which does not require a development treatment, in addition to the sulfonimide polymer in the composition, the composition is cured by light or heat as necessary. Such a compound and a reaction accelerator for accelerating the curing may be added. The light and / or thermosetting compound may be any of low molecular compounds, oligomers, and polymers containing at least one kind of the curable group. The light and / or thermosetting group refers to a functional group that cures the resin by at least one of heat and light. Specific examples of the “photo-curable functional group” and “thermo-curable functional group” include those having the same content as the above-described functional group which may be contained in the sulfonimide polymer skeleton and which can be cured by heat or light. .

As these curable compounds, there can be mentioned compounds usually used as a crosslinking agent. Specifically, compounds described in Shinzo Yamashita, Tosuke Kaneko, “Handbook of Crosslinking Agents” Taiseisha (1981), edited by the Society of Polymer Science, “Basic Edition of Polymer Data Handbook”, Baifukan (1986), etc. Can be used. For example, silane coupling agents such as organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc. Etc.), polyisocyanate-based compounds (e.g., toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate) Isocyanates, polymer polyisocyanates, etc.), polyblocked isocyanate compounds, polycarboxylic acid compounds and their carboxylic anhydrides (eg, phthalic acid, maleic acid, succinic acid, Rutaru acid, itaconic acid, pyromellitic acid, benzene 1,2,4,5-tetracarboxylic acid, 3,3 ', 4,
4′-benzophenonetetracarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, etc. and their anhydrides, etc.), polyol compounds (for example, 1,
4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.),

Polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Titanate coupling compounds (eg, tetrabutoxytitanate, tetrapropoxytitanate, isopropyl tristearoyl titanate, etc.), aluminum coupling compounds [eg, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate)] Etc.), polyepoxy group-containing compounds and epoxy resins [for example, those described in "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969), etc. Compounds), melamine resins (for example, compounds described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969), etc.), poly (meth) acrylate-based compounds (for example, Compounds described in No. Kawahara, Takeo Saegusa, Toshinobu Higashimura “Oligomer” Kodansha (published in 1976), Eizo Omori “Functional Acrylic Resin” Techno System (published in 1985), and the like. ,
Styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohols (for example, ethylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600,
1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane,
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers of pentaerythritol, or polyhydroxyphenols (eg, hydroquinone, resorcin, catechol and derivatives thereof):

Vinyl esters, allyl esters, vinyl amides or allyl amides of dibasic acids (for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.): polyamine ( For example, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and the like and a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid,
Condensates with crotonic acid, allyl acetic acid, etc., carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic acid,
Reactants of methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride and the like and alcohols or amines (for example, allyloxycarbonyl propionic acid, allyloxycarbonyl acetic acid, Ester derivatives or amide derivatives containing vinyl groups such as allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, itaconic acid) Allyl, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl methacrylate, vinyl acrylate Oxycarbonyl methyloxycarbonyl ethyl ester, N- diallylacrylamide,
N-allyl methacrylamide, N-allyl itaconamide, methacryloyl propionic allyl amide, etc.) or amino alcohols (for example, aminoethanol, 1-
Condensates of aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) with a carboxylic acid having a vinyl group.

Examples of the reaction accelerator for accelerating the curing reaction include thermal or photoradical polymerization initiators such as peroxides and azobis compounds, and organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, and the like). p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organic metal compounds (acetylacetonato zirconium salt,
Acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compound (diethyldithiocarbamate, etc.), thiuram disulfide compound (tetramethylthiuram disulfide, etc.), carboxylic anhydride (phthalic anhydride, maleic anhydride, etc.) , Succinic anhydride, butyl succinic anhydride, etc., 3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.). When the composition contains the curable group or the curable compound, the curing reaction is performed by applying light and / or light after applying the photosensitive composition.
Or by applying heat. In order to carry out thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional printing plate production. For example, when the drying conditions are high temperature and / or
Or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, 60 ° C to 150 ° C
For 5 to 120 minutes. When the above-described reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As the curing method, any of light and heat can be used, but a method using heat is more convenient and preferable. The amount of the curable group which can be cured by light or heat is 0 to 70% by weight, preferably 0 to 70% by weight based on the whole composition.
30% by weight. The amount of the curable compound which can be cured by light or heat is from 0 to 70% by weight, preferably from 0 to 30% by weight, based on the total composition. The amount of the reaction accelerator for accelerating the curing is from 0 to 20% by weight, preferably from 0 to 5% by weight, based on the whole composition. When the photosensitive composition according to the present invention is used after being coated, as a support,
A dimensionally stable plate is used. Examples of the dimensionally stable plate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), stainless steel, zinc, copper, etc. Metal plates such as, for example, plastics 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 of the film include a film, a paper or a plastic film on which the above-mentioned metal is laminated or vapor-deposited.

Among these supports, an aluminum plate is particularly preferable for preparing a photosensitive lithographic printing plate, because it is extremely stable in dimension and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film is also preferable. In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation treatment is performed. Is preferred. Other preferred supports can be any material that constitutes or manufactures capacitors, semiconductors, multilayer printed circuits or integrated circuits. In particular, thermally oxidized silicon materials and / or optionally doped aluminum-coated silicon materials, and other substrates common in semiconductor technology such as, for example, silicon nitride, gallium arsenide and indium phosphide. Can be mentioned. In addition, substrates known in the manufacture of liquid crystal displays, such as glass and indium tin oxide, as well as metal plates and foils (eg, aluminum, copper or zinc), double and triple metal foils, or metal deposited non-conductive sheets,
If desired, a SiO ₂ material coated with aluminum, paper and the like are suitable. These substrates may be subjected to thermal pretreatment, surface roughening, initial etching, or treatment with a reagent to improve desirable properties, such as enhancing hydrophilicity.

The photosensitive composition of the present invention may optionally contain
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a compound having two or more phenolic OH groups for promoting the solubility in a developer can be contained.
Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5
05 (all manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.
Further, the photosensitive composition of the present invention is sensitized to i or g by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used to a longer wavelength region than far ultraviolet where the photoacid generator has no absorption. Lines can be made sensitive. Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and pyrene. , Perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4 -Nitroaniline, N-acetyl-
p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3 -Diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), coronene and the like, but not limited thereto is not.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination. The concentration (total solid content including additives) in the above components is suitably 2 to 50% by weight.

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, and EFTOP EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173, F17
7 (Dai Nippon Ink Co., Ltd.), Florado FC430,
FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, S
C102, SC103, SC104, SC105, SC
Fluorinated surfactants such as No. 106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymerized polyflow No. 75, No. 95 ( Kyoeisha Oil & Fat Chemical Co., Ltd.) and the like. The content of these surfactants is 10% solids in the composition of the present invention.
It is usually at most 2 parts by weight, preferably at most 1 part by weight, per 0 parts by weight. These surfactants may be added alone or in some combination.

As the developer of the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkali such as sodium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium tertiary phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, aqueous ammonia , Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohols such as dimethylethanolamine and triethanolamine Alkaline aqueous solutions such as amines, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used. Further, an appropriate amount of an alcohol such as benzyl alcohol or a surfactant may be added to the above alkaline aqueous solution. The light source used for exposure of the photosensitive composition of the present invention includes, for example, ultrahigh-pressure, high-pressure, medium-pressure, and low-pressure mercury lamps, metal halide lamps, xenon lamps, chemical lamps, carbon arc lamps, and LD-excited Nd: YAG. , MPOA,
LD pumped Nd: YAG-SHG, He-Ne laser,
Ar laser, krypton ion laser, helium-
Infrared, visible, and ultraviolet lasers such as a cadmium laser and a KrF excimer laser, fluorescent lamps, dangsten light, and sunlight. Further, an electron beam, an X-ray, an ion beam, or the like can be used.

[0060]

Next, the present invention will be described in more detail with reference to examples. The percentage in the following examples is
All percentages are by weight unless otherwise specified. Example 1 A 0.30 mm thick aluminum plate was coated with a nylon brush and 40
The surface was sand-grained using a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. After being immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, it was washed with running water, then neutralized and washed with a 20% HNO ₃ aqueous solution, and washed with water. This was converted to 160 coulombs / dm in a 1% nitric acid aqueous solution using a sine wave alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with the quantity of electricity at the time of anode ² . When the surface roughness was measured, it was 0.6 μ (Ra indication).
After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, the thickness becomes 2.7 g / m ² at a current density of 2 A / dm ² in a 20% H ₂ SO ₄ aqueous solution. As described above. The following photosensitive solution was applied on the aluminum support thus obtained using a wheeler,
Dry at 0 ° C. for 2 minutes. -0.4 g of the sulfonimide polymer of Synthesis Example 1-2.0 g of m / p-cresol novolak resin (m / p ratio: 6: 4)-0.01 g of crystal violet-18 g of methyl ethyl ketone-6 g of 2-methoxyethanol Coating after drying The amount was 2.1 g / m ² . These photosensitive lithographic printing plates were each used with a Ushio Electric low pressure mercury lamp (UIS
L-112-01) and exposed through a pattern for 5 minutes. The optical density of the exposed part and the unexposed part was measured with a Macbeth densitometer, and the density difference was obtained. As a result, a clear print-out image having an optical density difference of 0.27 was obtained. Next, when the exposed photosensitive lithographic printing plate was immersed in a 4% aqueous solution of sodium metasilicate for 1 minute and developed, the exposed portion leached and a good image was obtained.

Example 2 4 g of a novolak resin composed of m-cresol / p-cresol = 45/55 and having a weight average molecular weight of 7,540 (in terms of polystyrene), 1 g of a dissolution inhibitor represented by the following structural formula [A-1], and The sulfonimide polymer of Synthesis Example 1 0.5
g was dissolved in 15 g of ethyl celloselv acetate and 0.2 g was dissolved.
A resist solution was prepared by filtration through a μm filter.
This resist solution was applied on a silicon wafer using a spin coater having a rotation speed of 2500 rpm,
Dry on a vacuum adsorption type hot plate at 0 ° C for 60 seconds,
A resist film having a thickness of 1.0 μm was obtained. In this resist film,
248 nm KrF excimer laser stepper (NA = 0.
Exposure was performed using (42). After exposure, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 100 ° C, and immediately 2.
38% tetramethylammonium hydroxide (TMA
H) Dipped in an aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. As a result, the optimal exposure amount was 35 mJ /
cm ² and a resolution of 0.40 μm.

[0062]

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Example 3 A meta-paracresol novolak resin 2.0 having a molecular weight of about 6000 and an m / p = 60/40 charge ratio, 0.8 g of a compound represented by the following structural formula [A-2], and a synthesis example 0.12 g of the sulfonimide polymer (1) was dissolved in 8.0 g of dimethylacetamide (DMAc) and filtered through a 0.4 μm membrane filter to obtain a photosensitive composition. Next, this solution was used to form a coating film on a silicon wafer, and 8000
膜 film was obtained. After exposure using the exposure apparatus described in Example 1, paddle development was performed for 45 seconds using a 1.19% aqueous TMAH solution as a developer, and the sensitivity, resolution, and residual film after development were measured. As a result, when the exposure amount was 45 mJ / cm ² , a resolution of 0.6 μ was given.

[0064]

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Example 4 Cresol novolak resin (m / p = 6/4; Mw = 4)
500), 0.5 g of Nicalac (registered trademark: manufactured by Sanwa Chemical Co., Ltd.) Mw30 having methylolated melamine as a main component as an acid crosslinking agent, and 0.1 g of the following sulfonimide polymer as a photoacid generator. A photoresist composition was prepared by dissolving in 17.0 g of ethyl cellosolve acetate and filtering this solution through a 0.2 μm microfilter. This photoresist composition was applied on a clean silicon wafer using a spinner, and dried on a hot plate at 90 ° C. for 60 seconds to obtain a 1 μm-thick resist film. This is then reduced by a projection exposure apparatus (i-line, numerical aperture 0.4).
In step 0), the exposure is changed stepwise through a resolution chart mask, and then exposure is performed with a hot plate at 100 ° C.
After heating for 2 seconds, the film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, washed with water for 30 seconds, and dried. The sensitivity was expressed as an exposure amount at which the residual film yield of the resist after development of the irradiated portion became 50%. The resolution was determined by scanning the fine pattern of the resist on the wafer obtained at the above exposure dose with a scanning electron microscope (S
EM), and the evaluation was performed with a minimum dimension at which the resist pattern was separated to the substrate surface. At the same time, the development residue generated between the patterns was observed and evaluated by visual evaluation on the screen. As a result, the exposure amount was 70 mJ / cm ² and the resolution was 0.55.
μm, and a pattern having no development residue was obtained.
Sulfonimide polymer used in Example 4

[0066]

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Example 5 A photosensitive solution having the following composition was applied on a 100 μm polyethylene phthalate film using a spinner, and dried at 100 ° C. for 2 minutes to form a photosensitive layer. The rotation speed of the spinner was 100 rotations / minute.・ 1.4 g of pentaerythritol tetraacrylate ・ 1.3 g of benzyl methacrylate and methacrylic acid copolymer (copolymerization molar ratio 73:27) ・ 0.4 g of the sulfonimide polymer of Synthesis Example 1 ・ 12 g of methyl ethyl ketone ・ propylene glycol monomethyl ether Acetate 12g Polyvinyl alcohol (degree of saponification 86.5)
A 3% by weight aqueous solution of -89 mol% and a degree of polymerization of 1000) was applied and dried at 100 ° C for 2 minutes. The photosensitive composition thus obtained was used as a low-pressure mercury lamp UISL-112-
01 (manufactured by Ushio Inc.), immersed in the following developer at 25 ° C. for 1 minute, and the amount of exposure until the exposed portion was no longer eluted was 5 mJ / cm ² .・ Sodium carbonate 10g ・ Butyl cellosolve 5g ・ 1 liter of water

Examples 6 and 7 On the same support as used in Example 1, the following photosensitive solutions A and B were applied at a rotation speed of 200 revolutions / minute using a wheeler, and dried at 100 ° C. for 1 minute. did. Photosensitive solution A (Example 6) 5 g of sulfonimide polymer of Synthesis Example 1 45 g of diethylene glycol dimethyl ether Photosensitive solution B (Example 7) 3.2 g of sulfonimide polymer of Synthesis Example 2 5 mg of phthalic anhydride 1 mg of orthochlorophenol Diethylene glycol dimethyl ether 27 g The photosensitive plate coated with the photosensitive solution B was further heated at 140 ° C. for 1 hour. Next, each was exposed to 5000 counts using an eye rotary printer (manufactured by Eye Graphics Co., Ltd.).
Printing was carried out using a Harris Aurelia 125 offset printing machine without development after exposure. 3000 prints were obtained on the printing plate to which the photosensitive liquid A was applied, and 4,000 were obtained for the printing plate to which the photosensitive liquid B was applied.

Examples 8 to 12 Styrene-butadiene resin (1
% Toluene solution Shell Petroleum Product name Calton 1300
x) was applied and heated at 170 ° C. A photosensitive solution containing the following sulfonimide polymer was coated on the support, dried at 100 ° C. for 1 minute, and further heated at 140 ° C. for 1 hour. Photosensitive solution: 3.2 g of sulfonimide polymer shown in Table 1. 5 mg of phthalic anhydride. 1 mg of orthochlorophenol. 30 g of tetrahydrofuran. The obtained printing original plate was subjected to a low-pressure mercury lamp (UISL manufactured by Ushio Inc.).
-112-01), and printing was performed using an offset printing machine (Ryobi 3200MCD) without development. Table 1 shows the number of obtained stain-free prints.

[0070]

[Table 1] Table 1 Example Sulfonimide polymer Number of printed sheets 8 S-8 5000 9 S -9 4500 10 S-10 6000 11 S-11 8000 12 S-12 5000 ──────────────────────────────

[0071]

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[0072]

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Examples 6 to 12 clearly show that by using the photosensitive composition containing a polymer having a sulfonimide group according to the present invention, a printing original plate requiring no development can be obtained.

[0074]

[Effect of the Invention] Excellent in safety, thermal stability and manufacturing suitability,
A printing original plate usable as a printing plate can be obtained without performing development processing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI H01L 21/027 H01L 21/30 502R (58) Investigated field (Int.Cl. ⁷ , DB name) G03F 7/038 G03F 7 / 004 G03F 7/00 503 G03F 7/028 G03F 7/039 H01L 21/027

Claims (1)

(57) [Claims] 1. A photosensitive composition containing a polymer having at least one sulfonimide group represented by the following general formula (1). ^{_{-L -SO 2 -NR 2 -SO 2 -R}} 1 (1) wherein R ¹ and R ² are each independently an aromatic group, substituted aromatic group, an alkyl group or a substituted alkyl group. L represents a linking group for linking a sulfonimide group to a polymer moiety.