JPS63121045A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having high photosensitivity and wide development latitude by incorporating two kinds of specified compds. and a high molecular compd. whose solubility in a developing soln. is increased by the action of an acid. CONSTITUTION:This photosensitive compsn. contains at least one kind of compd selected among 1,2-naphtoquinone-2-diazido-4-sulfonic ester compds. and 1,2- naphthoquionone-2-diazido-5-sulfonic ester compds. represented by formula I, a compd. capable of producing an acid on being irradiated with rays of active light and a high molecular compd. whose solubility in a developing soln. is increased by the action of the produced acid. The high molecular compd. has >=1mol% structural units derived from a monomer represented by formula II (where R1 is H, halogen or the like, each of R2-R4 is H, optionally substd. alkyl, aryl or the like, A is a single bond, -O-R6-CO- or the like and R6 is bivalent aliphat. or arom. hydrocarbon).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a positive photosensitive composition suitable for the production of lithographic printing plates, multicolor printing proofs, drawings for overhead projectors, IC circuits, and photomasks. relating to things. More specifically, the present invention relates to a photosensitive composition containing an orthoquinone diazide compound as a photosensitive component.

[Conventional technology]

Orthoquinone diazide compounds have been known as so-called positively acting photosensitive substances that are solubilized by actinic rays, and have actually been widely used in lithographic printing plates, photoresists, and the like.

Examples of such orthoquinone diazide compounds include, for example, U.S. Pat. Nos. 2,766,118 and 2,767.
No. 092, No. 2.772,972, No. 2.859
, No. 112, No. 2.907.665, No. 3,04
No. 6.110, No. 3.046,111, No. 3.0
46.115, 3.046.118, 3.
No. 046,119, No. 3.046.120, No. 3
．． 046.121, 3.046.122, 3,046.123, 3.061.430, 3.102.809, 3.106.465,
It is described in numerous publications, including the publications No. 3.635.709 and No. 3.647.443.

These orthoquinonediazide compounds are decomposed by irradiation with actinic rays to produce a five-membered carboxylic acid, which makes them soluble in alkali, but all of them have the disadvantage of insufficient photosensitivity. have This is because, in the case of orthoquinone diazide compounds, the quantum yield essentially does not exceed 1.

Various attempts have been made to increase the photosensitivity of photosensitive compositions containing orthoquinonediazide compounds, but it has been extremely difficult to increase photosensitivity while maintaining development tolerance during development. . For example, examples of such attempts include Japanese Patent Publication No. 48-12242 and Japanese Patent Publication No. 5
Examples include contents described in publications such as No. 2-40125 and U.S. Pat. No. 4.307.173.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel photosensitive composition in which these problems are solved. That is, the object of the present invention is to provide a novel photosensitive composition that has high photosensitivity and wide development latitude during development.

Yet another object of the present invention is to provide a novel photosensitive composition that is simple to manufacture and easily obtainable.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the present inventors discovered that the above object could be achieved by using a novel positive-type photosensitive composition, and arrived at the present invention.

That is, the present invention provides (a) a 1,2-naphthoquinone-2-diazido-4-sulfonic acid ester compound and a 1,2-naphthoquinone-2-diazido-5-sulfonic acid ester compound represented by the following general formula (I). At least one type of flower stand selected from the group consisting of [compound (a)], (b) a compound capable of generating an acid upon irradiation with actinic light [compound (b)), and (C) the following general formula (I A photoresist containing a polymer compound [compound (C)] having at least 1 mol% of a structural unit derived from the monomer represented by [) and whose solubility in a developer increases by the action of an acid. A composition is provided.

In the formula, R represents a monovalent aliphatic or aromatic hydrocarbon.

R1 represents a hydrogen atom, a halogen, or an alkyl group which may have a substituent. Preferably a hydrogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom or a methyl group. R2, R3, and R may be the same or different, and each represents a hydrogen atom, alkyl, aryl, or aralkyl that may have a substituent, or -0R3. Preferably, it represents an alkyl, aryl, or aralkyl group that may have a substituent. R3 represents an alkyl, aryl, or aralkyl group which may have a substituent. Preferably, it represents an alkyl group having 1 to 8 carbon atoms or an alkyl group having 6 to 15 carbon atoms. A represents a single bond, -0-R, -CO-1, or an optionally divalent aliphatic or aromatic hydrocarbon.

R is a hydrogen atom, alkyl which may have a substituent,
Indicates aryl, aralkyl, or -〇〇-RS. Preferably a hydrogen atom, an alkyl having 1 to 4 carbon atoms,
Or -Go-R.

shows. R. represents an alkyl, aryl, or aralkyl group that may have a substituent. Preferably, it represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.

The compound represented by the general formula (I) used in [al] of the present invention generally has a halogenosulfonyl group such as sulfonyl chloride at the 4th or 5th position.

It can be expressed as a sulfonic acid ester compound obtained by chemical condensation of a 2-naphthoquinone-2-diazide compound and a mono- or polyhydroxyphenyl compound. Therefore, R in -C formula (I) represents the residue of a mono- or polyhydroxyphenyl compound to be condensed.

Examples of such mono- or polyhydroxyphenyl compounds include 2.2'-dihydroxy-diphenyl;2', 4. 4'-tetrahydroxydiphenyl, 2,3-dihydroxynaphthalene, 2
, 3.4-1 lyhydroxybenzophenone, 2.2',
4.4'-tetrahydroxybenzophenone, pt-
Examples include butylphenol, and there are many other examples. Among them, relatively high molecular weight compounds such as phenol-formaldehyde resins or 0-, m-, or p-talesol-formaldehyde resins described in U.S. Pat. No. 3,046,120 are film-forming. It is excellent in terms of high properties and is suitable for the compound (a) of the present invention.

Also, JP-A-56-1045 and JP-A-56-1045
Condensates of polyhydric phenols and aldehydes/ketones disclosed in Japanese Patent Publication No. 1044, Japanese Patent Publication No. 43-28403, Japanese Patent Publication No. 49-24361, etc.;
Co-condensates of catechol, resorcinol, or hydroquinone and substituted phenols with aldehydes and ketones disclosed in JP-A No. 9-84238 and JP-A-59-84239; substitutions described in JP-A-60-31138; In addition to condensates of phenol and benzaldehyde, cocondensates of phenol and substituted phenols such as 0-, m-, or p-cresol with aldehydes and ketones, p-
Hydroxystyrene polymers and the like are also compounds (a) of the present invention.
It is effectively used for

The preferred content of the compound (al) of the present invention is 5 to 40 wt% based on the total solid content of the photosensitive composition.

Compounds that can generate acids upon irradiation with actinic rays include many known compounds and mixtures, such as diazonium, phosphonium, sulfonium, and iodonium BP, -, PF.

SbF&-, 5iFb-, Cj! Salts such as 04-, organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable. Of course, U.S. Patent No. 3.779.778
Also suitable as compound (b) are the compounds which generate acids by photolysis as described in German Patent Application No. 2,610,842. Furthermore, compounds intended to provide a visible contrast between the unexposed area and the exposed object during exposure in combination with a suitable dye, such as JP-A-55-77
Compounds described in Publications No. 742 and No. 57-163234 can also be used as compounds).

Among the above-mentioned compounds capable of generating acid through photolysis, typical ones will be explained below.

(I) The following general formula (II) substituted with a trihalomethyl group
I) Oxadiazole 3M "4 body or -
1 5-1-Ryazine derivative represented by formula (IV) where R1 represents a substituted or unsubstituted aryl or alkenyl group, R1° represents R,, -cxi or a substituted or unsubstituted alkyl group . X represents a chlorine atom or a bromine atom.

Specifically, the following may be mentioned.

(I[[-1) (I[-2) (I[[-3) (II[-4) (It-5) ([[[-6) (III-7) (I[[-8) (TV-1) (IV-2) (IV-3) (IV-4) (IV-5) (IV-6) (IV-7) CC1° (IV-8) CC1° (It/-9) CN3 CI (2) An iodonium salt represented by the following general formula (V) or a sulfonium salt represented by the general formula (Vl), where Ar15 Art in the formula may be the same or different, and may be substituted or unsubstituted. Indicates an aromatic group. R11, R1
□ and R11 may be the same or different and represent a substituted or unsubstituted alkyl group or aromatic group. X- is BFh-, P
Fi-, ASF&-, 5bFh-, CJ! 04- is shown.

Also, two of R, , R, t, R, and Ar,
, Ar2 may each be bonded via a single bond or a substituent.

-C Compounds represented by formula (V) include, for example, JP-A-50-158680, JP-A-51-100716,
and compounds described in Japanese Patent Publication No. 52-14277. Further, as the compound represented by the general formula (Vl), for example, JP-A No. 51-56885, JP-A No. 52-14
No. 278, US Pat. No. 4,442.197, and West German Patent No. 2.904,626.

Specifically, the following are included.

(V-1) (V-2) (V-3) (V-4) (V-5) (V-6) (V-7) (V-8) (V-9) (V-10) (V-11) + (V-12) + (Vl-1) (V[-2) (Vl-3) (Vl-4) (V[-5) (Vl-6) (VI-7) ( Vl-8) (Vl-9) (VI-10) (VI-11) (VI-12) (Vl-13) (Vl-14) (Vl-15) (3) In the following general formula (■) A disulfone derivative represented by the formula (■) or an imidosulfonate derivative represented by the general formula (■) Arc SOx SO2Ar4 (■) Represents a ryl group.

R14 represents a substituted or unsubstituted alkyl or aryl group. Z represents a substituted or unsubstituted alkylene, alkenylene, or arylene group.

Specifically, the compounds shown below are mentioned.

(■-1) (■-2) (■-3) (■-4) (■-5) (■-6) (■-7) (■-1) (■-4) (■-5) (■-6) (■-7) (■-8) (■-9) (■-10) (■-11) (■-12) The content of the compound (b) of the present invention is 0.01 to 10 wt% based on the total solid content of the composition, preferably 0
．． 1 to 8 t%.

Standing (9) -i formula (n) constituting the polymer compound of the present invention (C)
Examples of monomers represented by include the following.

(II-1) (n-2) (n-3) (n-4) (n-5) (n-6) (n-7) \. H3 (II-8) (n-9) (II-10) , tl S (n-11) (II-12) (II-13) (n-14) (n-15) H2 (n-16) (If-17) (II-19) (II-20) (II-21) (n-22) (II-23) Note that R in the specific examples represents a hydrogen atom or a methyl group.

The polymer compound used in the present invention (c) has the general formula (I
It can be used as a homopolymer of the monomer shown in f), but it can also be used in the form of a two or more copolymer with another polymerizable compound having an ethylenically unsaturated bond (Type I or more). It's okay.

Suitable compounds having a polymerizable ethylenically unsaturated bond include those shown below.

For example, a compound having one addition-polymerizable unsaturated bond selected from acrylic esters, acrylamide frames, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, etc. It is. Specifically, examples include acrylic esters such as alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylates (such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic amyl acid, ethylhexyl acrylate, octyl acrylate,
t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate-1-12,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate,
glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate,
tetrahydrofurfuryl acrylate, etc.), aryl acrylates (e.g. phenyl acrylate, etc.);
Methacrylic acid esters, such as alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate) , benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol mono methacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), oryl methacrylate (e.g., phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, etc.), acrylamides, such as acrylamide, N-alkylacrylamide, (the alkyl group Examples include those having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc. ), N
-arylacrylamide, (as the nucleol group,
Examples include phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, and hydroxyphenyl group. ), N, N-dialkylacrylamide (the alkyl group includes those having 1 to 10 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N
-arylacrylamide (such aryl groups include, for example, phenyl groups), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-
acetylacrylamide, etc.; methacrylamides, such as methacrylamide, N-alkyl methacrylamide (the alkyl group includes those having 1 to 10 carbon atoms,
Examples include methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, and cyclohexyl group. ), N-arylmethacrylamide (the aryl group includes phenyl group, hydroxyphenyl group, etc.), N,N-dialkylmethacrylamide (
Examples of the alkyl group include ethyl group, propyl group, and butyl group. ) N,N-diarylmethacrylamide (the aryl group includes a phenyl group, etc.),
N-hydroxyethyl-N-methylmethacrylamide,
N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc.; allyl compounds, such as allyl esters (such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl valmitate, stearin); vinyl ethers, such as alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloro); Ethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. ), vinyl ethers (e.g. vinyl phenyl ether, vinyl tolyl ether, vinyl chlorphenyl ether, vinyl
vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl Chloracetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl 7acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, Vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.; styrenes, such as styrene, alkylstyrenes (such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclo (hexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.)
, alkoxystyrene (e.g. methoxystyrene, 4-
methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrenes (e.g. chlorstyrene, dichlorostyrene, trichlorstyrene, tetrachlorostyrene, pentachlorstyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene) styrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.); crotonate esters, such as alkyl crotonate (e.g. butyl crotonate, hexyl crotonate, glycerin monocrotonate); Dialkyl itaconates (e.g. dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); Dialkyl maleic acid or fumarate (e.g. dimethyl maleate, dibutyl fumarate, etc.); Acrylic acid, methacrylic acid, acrylonitrile , methacrylonitrile, etc. In addition, addition polymerizable unsaturated compounds that are generally copolymerizable with the compound represented by the general formula (n) may be used.

The content of the polymer compound (C) of the present invention is 5 to 95-t%, preferably 10 to 95-t%, based on the total solid content of the photosensitive composition.
70 days t%.

The photosensitive composition of the present invention can be used with only the above-mentioned compounds (a1, (bl and (C)), but is preferably used in a composition further containing an alkali-soluble resin.

Suitable alkali-soluble resins include novolac-type phenolic resins, specifically phenol-formaldehyde resins, 0-talesol-formaldehyde resins 11, m-
Cresol-formaldehyde resin, p-talesol-
Examples include formaldehyde resins and co-condensates thereof. Furthermore, acrylic resins, methacrylic resins, polyurethane resins, polyvinyl acecool resins, -polystyrene resins, and the like having carboxyl groups or phenol groups can also be used. Two or more of these resins may be used in combination.

When the alkali-soluble resin is contained, its content is 30 to 90 wt%, preferably 50 to 80 wt%, based on the total solid content of the photosensitive composition.

The photosensitive composition of the present invention may further contain dyes, pigments, plasticizers, compounds that increase the acid generation efficiency of the acid-generating compound (so-called sensitizer), etc., as necessary. . Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green BG, oil blue BO3, oil blue #6
03, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.) Crystal Bioleft (c) 42555),
Methyl violet (c) 42535), Rhodamine B
(CI45170B) Malachite Green (CI42
000), methylene blue (CI52015), etc.

The photosensitive composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, Examples include toluene and ethyl acetate, and these solvents can be used alone or in combination. The concentration of the above components (total solid content including additives) is 2 to 50 wt%. The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3.0 g-n.
f is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosensitive composition of the present invention, the support may be an aluminum plate treated with hydrophilic treatment, such as a silicate-treated aluminum plate, an anodized aluminum plate, or a grained aluminum plate. There are plates, silicate electrodeposited aluminum plates, surface lead plates, stainless steel plates, chrome-treated mesh plates, hydrophilic treated plastic films and paper.

Supports suitable for producing printing proof plates, films for overhead projectors, and films for second originals include transparent films such as polyethylene terephthalate film and triacetate film, and the surfaces of these plastic films are matted chemically or physically. I can give you what I have transformed into. Supports suitable for producing photomask films include polyethylene terephthalate films deposited with aluminum, aluminum alloys, and chromium, and polyethylene terephthalate films provided with colored layers.

The photosensitive composition of the present invention can also be used as a photoresist by coating it on various supports other than those mentioned above, such as copper plates, copper-plated plates, and glass plates.

Examples of the active light layer used in the present invention include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Such laser beams include helium neon lasers, argon lasers, krypton ion lasers, and helium neon lasers.
Examples include cadmium lasers.

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

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

〔Example〕

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

Synthesis example (synthesis of copolymer of compound example (II-8) (R=CH) and benzyl methacrylate) 35.3 g (0°160 mol) of dimethylphenylsilyl methacrylate
, benzyl methacrylate 7.1 g (0,040 mol)
120ml of 2-methoxyethanol! After heating to 70°C under a nitrogen stream, 0.25 g of α,α'-azobisisobutyronitrile was added and a polymerization reaction was carried out for 8 hours.

After the reaction is complete, add 3I of water to the reaction solution! The resulting white precipitate was filtered and dried to obtain 38.3 g of copolymer.
I got it.

A 2S aluminum plate with a thickness of 0.24 irises was immersed in a 10% aqueous solution of tertiary sodium phosphate for 3 minutes to degrease it, and then grained with a nylon brush. The film was etched with sodium chloride for about 10 seconds, and then desmutted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dII+'' for 2 minutes to produce an aluminum plate.

Next, four types of photosensitive liquids (A)-1 to (A)-4 were prepared by changing the type of compound (C) of the present invention in photosensitive liquid (A) below, and this photosensitive liquid was anodized. Each of the photosensitive planographic printing plates (A)-1 to (A)-4 was prepared by applying the coating onto an aluminum plate and drying at 100° C. for 2 minutes. All coating amounts at this time are dry weight. It was Og/rd.

The compounds (C) of the present invention used in photosensitive solutions (A)-1 to (A)-4 are shown in Table 1.

Photosensitive liquid (A) Next, as a comparative example, the following photosensitive liquid CB) was applied in the same manner as photosensitive liquid (A) to prepare a photosensitive planographic printing plate (B).

Photosensitive liquid (B) The coating weight after drying is 2. It was Og/rd. A gray scale with a density difference of 0.15 was brought into close contact with the photosensitive layer of photosensitive lithographic printing plates (A)-1 to (A)-4 and CB), and exposed from a distance of 70 cm using a 30 ampere carbon arc lamp. went.

The photosensitive lithographic printing plates (A)-1 to (A)-4 and (B) which were exposed to show the excellent photosensitivity of the present invention were DP-4.
(Product name: manufactured by Fuji Photo Film ■) was immersed and developed for 60 seconds at 25°C with an 8-fold diluted aqueous solution, and the exposure time was determined to make the 5th stage completely clear on a gray scale with a density difference of 0.15. The results are as shown in Table 1.

As can be seen from Table 1, all of the photosensitive planographic printing plates (A)-1 to (A)-4 using the compound (C) of the present invention have a shorter exposure time and higher sensitivity than (B).

The molecular weight of the compound (C) of the present invention in Table 1 was determined by gel permeation chromatography (polystyrene standard), and the weight average molecular weight was 20,000 in all cases.
~50,000.

Furthermore, in order to demonstrate the excellent development tolerance of the present invention, a gray scale with a density difference of 0.15 was closely adhered to the photosensitive layer of the photosensitive lithographic printing plates (A)-1 to (A)-4 and CB). Exposure was performed for 30 seconds from a distance of 70 cm using an ampere carbon arc lamp.

The exposed photosensitive lithographic printing plates (A)-1 to (A)-4 and (B) were immersed and developed in the same developer as in Example 1 at 25° C. for 60 seconds and 3 minutes. Table 2 shows the difference in the number of completely clear steps when developing for 60 seconds and 3 minutes on a gray scale with a density difference of 0.15.

Table 2 As can be seen from Table 2, the photosensitive lithographic printing plates (A)-1 to (Al-4) using the compound (C) of the present invention were all clear with small changes in the number of gray scale steps in some parts. , high development tolerance.

Claims (1)

[Claims] (a) 1,2-naphthoquinone-2-diazido-4-sulfonic acid ester compound and 1,2-naphthoquinone-2-diazido-5-sulfonic acid ester represented by the following general formula (I) At least one compound selected from the group consisting of compounds. (b) a compound capable of generating an acid upon irradiation with actinic rays, and (c) having at least 1 mol% of a structural unit derived from a monomer represented by the following general formula (II), and its solubility in a developer. 1. A photosensitive composition containing a high molecular compound whose properties are increased by the action of an acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, R represents a monovalent aliphatic or aromatic hydrocarbon. R_1 represents a hydrogen atom, a halogen, or an alkyl group which may have a substituent. R_2, R_3, R_4
may be the same or different, and each represents a hydrogen atom, alkyl, aryl, or aralkyl that may have a substituent, or -OR_5. R_5 represents an alkyl, aryl, or aralkyl group that may have a substituent. A indicates a single bond, -O-R_6-CO-, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_
6 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. R_7 represents a hydrogen atom, alkyl, aryl, or aralkyl which may have a substituent, or -CO-R_8. R_8 represents an alkyl, aryl, or aralkyl group that may have a substituent.