JP3206989B2 - Positive photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can form a fine resist pattern when manufacturing a lithographic printing plate, a proof print of multicolor printing, a drawing for an overhead projector, and an integrated circuit of a semiconductor device. The present invention relates to a positive photosensitive material .

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive material for solving the above problems. That is, it is an object of the present invention to provide a novel positive photosensitive material which has high photosensitivity and can be used in a wide range of wavelength light. A further object of the present invention is to provide a positive photosensitive material having a large difference in solubility between an exposed portion and an unexposed portion and a high development latitude.

[0003]

Means for Solving the Problems The present inventor has conducted a search for a novel positive photosensitive composition which can replace orthoquinonediazide in order to achieve the above object. As a result, the present inventors have found that two or more enol ethers such as vinyl ether groups are present. When a compound containing a group and, for example, a hydroxyl group-containing acrylic resin are prepared by diluting with a solvent, and coated and dried on a support, the above components are effectively thermally crosslinked by drying heat, and are insoluble in an alkaline aqueous solution, a solvent, or the like. In addition, the inventors found that the thermally crosslinked portion was efficiently hydrolyzed and solubilized in the presence of an acid, thereby completing the present invention. That is, the present invention provides (a) a compound having at least two enol ether groups represented by the following general formula (I), (b) a linear polymer having an acid component and a hydroxyl group, (c) an actinic ray or A solution containing a compound that is decomposed by irradiation with radiation to generate an acid is placed on a support.
In the positive photosensitive material obtained by coating and drying,
Apply heat during coating drying, or after coating drying and before the image exposure process.
To provide a positive photosensitive material characterized in that the component (a) is crosslinked with the component (b).
You. This photosensitive material has high sensitivity to ultraviolet light, visible light, electron beam or X-ray, and can form a clear positive image under a wide range of developing conditions .

The present invention relates to the above (a), (b) and (c)
It is a positive photosensitive material comprising a ternary, but first feature in that the linear polymer component enol ether group-containing compound and the components (a) (b) making a thermally crosslinked structure is there. First, the enol ether group-containing compound of the component (a) of the present invention will be described. In the enol ether group of the general formula (I), when R ₁ , R ₂ and R ₃ are an aryl group, they generally have 4 to 20 carbon atoms, and include an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
It may be substituted by an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. When R ₁ , R ₂ and R ₃ represent an alkyl group, they represent a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, and include a halogen atom, a cyano group, an ester group, It may be substituted by an oxy group, an alkoxy group, an aryloxy group or an aryl group. Also, R
_1, R ₂ and usually 3-8 when any two of R ₃ to form a cycloalkyl group or cycloalkenyl group attached, preferably a 5 or 6 ring members. In the present invention, among the enol ether groups represented by the general formula (I), preferred is an enol ether in which one of R ₁ , R ₂ and R ₃ is a methyl group or an ethyl group, and the remainder is a hydrogen atom. More preferred are vinyl ether groups wherein R ₁ , R ₂ and R ₃ are all hydrogen. In the present invention, various compounds containing two or more enol ether groups can be used, and these are compounds having a boiling point of 60 ° C. or more at atmospheric pressure, and the component (a)
Preferred compounds of the following general formula (II) or (II)
And vinyl ether compounds represented by I).

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive composition for solving the above problems. That is, an object of the present invention is to provide a novel positive photosensitive composition which has high photosensitivity and can be used in a wide range of wavelengths of light. A further object of the present invention is to provide a positive photosensitive composition having a large difference in solubility between an exposed portion and an unexposed portion and a high development latitude.

[0006]

Means for Solving the Problems The present inventor has conducted a search for a novel positive photosensitive composition which can replace orthoquinonediazide in order to achieve the above object. As a result, the present inventors have found that two or more enol ethers such as vinyl ether groups are present. When a compound containing a group and, for example, a hydroxyl group-containing acrylic resin are prepared by diluting with a solvent, and coated and dried on a support, the above components are effectively thermally crosslinked by drying heat, and are insoluble in an alkaline aqueous solution, a solvent, or the like. In addition, the inventors found that the thermally crosslinked portion was efficiently hydrolyzed and solubilized in the presence of an acid, thereby completing the present invention. That is, the present invention relates to the following (a):
(B) a linear polymer having an acid component and a hydroxyl group, and (c) a compound which decomposes upon irradiation with actinic rays or radiation to generate an acid. A positive photosensitive composition characterized in that the component (a) and the component (b) are cross-linked by heat, showing high sensitivity to ultraviolet light, visible light, electron beam or X-ray, The present invention also relates to a photosensitive composition capable of forming a clear positive image under a wide range of developing conditions.

[0007]

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In the formula, R ₁ , R ₂ and R ₃ represent hydrogen, an alkyl group or an aryl group, which may be the same or different. Also, two of them may combine to form a saturated or olefinically unsaturated ring. Hereinafter, the present invention will be described in detail.

The present invention relates to the above (a), (b) and (c)
There is a positive photosensitive composition composed of the three components described above. The first characteristic is that the enol ether group-containing compound of the component (a) and the linear polymer of the component (b) thermally form a crosslinked structure. There is. First, the enol ether group-containing compound of the component (a) of the present invention will be described. In the enol ether group of the general formula (I), when R ₁ , R ₂ and R ₃ are an aryl group, they generally have 4 to 20 carbon atoms, and include an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
It may be substituted by an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. When R ₁ , R ₂ and R ₃ represent an alkyl group, they represent a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, and include a halogen atom, a cyano group, an ester group, It may be substituted by an oxy group, an alkoxy group, an aryloxy group or an aryl group. Also, R
_1, R ₂ and usually 3-8 when any two of R ₃ to form a cycloalkyl group or cycloalkenyl group attached, preferably a 5 or 6 ring members. In the present invention, among the enol ether groups represented by the general formula (I), preferred is an enol ether in which one of R ₁ , R ₂ and R ₃ is a methyl group or an ethyl group, and the remainder is a hydrogen atom. More preferred are vinyl ether groups wherein R ₁ , R ₂ and R ₃ are all hydrogen. In the present invention, various compounds containing two or more enol ether groups can be used, and these are compounds having a boiling point of 60 ° C. or more at atmospheric pressure, and the component (a)
Preferred compounds of the following general formula (II) or (II)
And vinyl ether compounds represented by I).

[0010]

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Here, A represents an m-valent alkyl group, an aryl group or a heterocyclic group, and B represents -CO-O-, -NHCOO- or-.
NHCONH-, R ₄ represents a linear or branched alkylene group having 1 to 10 carbon atoms, n is an integer of 0 or 1 to 10, m
Represents an integer of 2 to 6. The compound represented by the general formula (II) is described, for example, in Stephen. C. Lapin, Polymers Paint Color
Journal, 179 (4237), 321 (1988), that is, by the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or the reaction of a polyhydric alcohol or polyhydric phenol with a halogenated alkyl vinyl ether. can do. Specific examples include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, and hexanediol dihexane. Vinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether,
Solver pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene Vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,2-di (vinyl ether methoxy) benzene, 1,2-di (vinyl ether ethoxy) benzene, and compounds represented by the following general formulas (II-1) to (II-41) But not limited thereto.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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On the other hand, the compound represented by the general formula (III) (when B = CO—O—) can be produced by reacting a polycarboxylic acid with a halogenated alkyl vinyl ether. Specific examples include diethylene vinyl ether terephthalate, diethylene vinyl ether phthalate, diethylene vinyl ether isophthalate, dipropylene vinyl ether phthalate, dipropylene vinyl ether terephthalate, dipropylene vinyl ether isophthalate, diethylene vinyl ether maleate, diethylene vinyl ether fumarate, diethylene itaconate Examples thereof include vinyl ether, but are not limited thereto. Further, as the vinyl ether group-containing compound suitably used in the present invention, the following general formula (IV):
Examples of the compound include a vinyl ether group-containing compound synthesized by reacting a vinyl ether compound having an active hydrogen represented by (V) or (VI) with a compound having an isocyanate group.

[0026]

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Here, R ¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. As the compound containing an isocyanate group, for example, the compounds described in Handbook of Crosslinking Agents (published by Taisei, 1981) can be used. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-
Polyisocyanate type such as tolylene diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane, adduct of hexamethylene diisocyanate and water, xylene A polyisocyanate adduct type such as an adduct of isocyanate and trimethylolpropane can be used.

By reacting the above-mentioned isocyanate group-containing compound with an active hydrogen-containing vinyl ether compound, various compounds having a vinyl ether group at the terminal can be obtained.
Examples of the compound having a vinyl ether group used in the present invention are listed below, but the scope of the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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The compounds having at least two vinyl ether groups described above can be used alone, but may be used as a mixture of several kinds. The amount of the compound containing a vinyl ether group in the photosensitive composition is generally in the range of 1 to 80% by weight, preferably 5 to 50% by weight, based on the total solid content of the photosensitive composition. The linear polymer (b) having an acidic component and a hydroxyl group used in the present invention is thermally crosslinked with the compound (a) having at least two enol ether groups, and the crosslinked portion is efficiently decomposed by an acid. Any one can be selected and used. The linear polymer can be generally synthesized by a known method for obtaining a linear polymer. For example, a vinyl monomer having an acidic component, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, and a hydroxyl group are used. Can be obtained by copolymerizing a vinyl monomer having If necessary,
Further, another vinyl monomer may be copolymerized. Examples of the vinyl monomer containing an acidic component include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, isocrotonic acid, p-vinylbenzoic acid, p-vinylbenzenesulfonic acid, p-vinylcinnamic acid, and maleic acid. Monomethyl ether, maleic acid monoethyl ether and the like can be mentioned.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, p-2-hydroxyethylstyrene, N- (2-hydroxyethyl) maleimide, p-hydroxystyrene, (4-hydroxyphenyl) methacrylamide and the like. Other monomers copolymerizable with the above monomers include, for example, acrylonitrile, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, styrene, benzyl acrylate,
Benzyl methacrylate, vinyl benzoate, vinyl chloride, vinylidene chloride, vinyl acetate, N- (4-
(Sulfamoylphenyl) methacrylamide, N-phenylphosphonylmethacrylamide, butadiene, chloroprene, imeprene and the like. The preferred copolymerization ratio of the vinyl monomer containing an acidic component, the vinyl monomer containing a hydroxyl group, and another copolymerizable monomer is 5 to 80: 2 to 80: 0 to 97% by weight.
Range.

Although these linear polymers can be used alone, they may be used as a mixture of several kinds. The amount of the linear polymer added to the photosensitive composition is generally in the range of 1 to 95% by weight, preferably 20 to 90% by weight, based on the total solid content of the photosensitive composition. The molecular weight of linear polymers is generally 1,00
It is from 0 to 1,000,000, preferably from 1,500 to 200,000.
Further, as the linear polymer used in the present invention, one having an acid component and a hydroxyl group in one linear polymer chain as described above is preferable, but the same effect can be obtained with a specific developing solvent. It can also be obtained as a mixture of a linear polymer having a component and a linear polymer having a hydroxyl group. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, and a photodiscoloration agent. An agent, a compound that generates an acid by light known in the art such as a micro resist, and a mixture thereof can be appropriately selected and used.

For example, SI Schlesinger, Photogr. Sc
i. Eng., 18, 387 (1974), TS Bal et al, Polymer,
21, 423 (1980), etc., U.S. Pat.Nos. 4,069,055, 4,069,056, Re 27,992, ammonium salt described in Japanese Patent Application No. 3-140140, etc., DC Necker et al, Macromolecules, 17, 2468
(1984), CS Wen et al, Teh, Proc. Conf.
ing ASIA, p478 Tokyo, Oct (1988), US Patent 4,069,0
Nos. 55 and 4,069,056, etc., and the phosphonium salts described in JV Crivello et al, Macromorecules, 10 (6), 1
307 (1977), Chem. & Eng. News, Nov. 28, p31 (198
8), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150848, Iodonium salts described in the specification or JP-A-2-296514, JV Criv
ello et al, Polymer J. 17, 73 (1985), JV Crivel
lo et al. J. Org.Chem., 43, 3055 (1978), WR Wa
tt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1
789 (1984), JV Crivelloet al, Polymer Bull., 1
4, 279 (1985), JV Crivello et al, Macromorecul
es, 14 (5), 1141 (1981), JV Crivello et al, J. P.
olymer Sci., PolymerChem. Ed., 17, 2877 (1979),
European Patent Nos. 370,693, 3,902,114, 233,567
Nos. 297,443 and 297,442; U.S. Pat.No.4,933,37
No. 7, No. 161,811, No. 410, 201, No. 339,049, No.
4,760,013, 4,734,444, 2,833,827, German Patent No. 2,904,626, 3,604,580, 3,604,581

[0037] JV Crivello et al, Macromorecules,
10 (6), 1307 (1977), JV Crivello et al, J. Polym
er Sci., Polymer Chem. Ed., 17, 1047 (1979) and the like, CS Wen et al, Teh, Proc. Co.
Onium salts such as arsonium salts described in nf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
No. 815, JP 46-4605, JP 48-36281, JP
No. 55-32070, JP-A-60-239736, JP-A-61-169835
No., JP-A-61-169837, JP-A-62-58241, JP-A-62
-212401, JP-A-63-70243, JP-A-63-298339, the organic halogen compounds described in the specification or the gazette of K. Mei
er et al, J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al, Inorg. Chem., 19, 3007 (1980), D. Ast.
ruc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-1
Organometallic / organic halides described in 61445
S. Hayase et al, J. Polymer Sci., 25, 753 (1987),
E. Reichmanis et al, J. Polymer Sci., Polymer Che
m. Ed., 23, 1 (1985), QQ Zhu et al, J. Photoch
em., 36, 85, 39, 317 (1987), B. Amit et al, Tetrah
edron Lett., (24) 2205 (1973).

DHR Barton et al, J. Chem Soc., 3
571 (1965), PM Collins et al, J. Chem. Soc., Per
kin I, 1695 (1975), M. Rudinstein et al, Tetrahed
ronLett., (17), 1445 (1975), JW Walker et al,
J. Am. Chem. Soc., 110, 7170 (1988), SC Busman
et al, J. Imaging Technol., 11 (4), 191 (1985), H.
M. Houlihan et al, Macoromolecules, 21, 2001 (198
8), PM Collinset al, J. Chem. Soc., Chem. Commu
n., 532 (1972), S. Hayase et al, Macromolecules,
18, 1799 (1985), E. Reichmanis et al, J. Electroch
em. Soc., Solid State Sci. Technol., 130 (6), FM
Houlihan et al, Macromolecules, 21, 2001 (1988),
European Patent Nos. 0290,750, 046,083, 156,535,
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,710
No. 4,181,531, JP-A-60-198538, JP-A-53-1
Photoacid generator having an o-nitrobenzyl-type protecting group described in the specification or publication of No. 33022, M. TUNOOKA et al, Po.
lymer Preprints Japan, 38 (8), G. Berner et al, J.
Rad. Curing, 13 (4), WJ Mijs et al, Coating Tech
nol., 55 (697), 45 (1983), Akzo, H. Adachi et al, P
olymer Preprints, Japan, 37 (3), European Patent 0199,672
Nos. 84515, 199,672, 044,115, 010
No. 1,122, U.S. Pat.Nos. 4,618,564, 4,371,605,
No. 4,431,774, JP-A-64-18143, JP-A-2-245756
, A compound which generates sulfonic acid upon photodecomposition, such as iminosulfonate described in Japanese Patent Application No. 3-140109 or the specification, etc., described in JP-A-61-166544. Disulfone compounds can be mentioned.

Compounds in which an acid-generating group or compound is introduced into the main chain or side chain of the polymer, for example, ME Woodhouse et al, J. Am. Chem.
c., 104, 5586 (1982), SP Pappas et al, J. Imagin
g Sci., 30 (5), 218 (1986), S. Kondo er al. Makromo
l. Chem., Rapid Commun., 9,625 (1988), Y. Yamada e
t al, Makromol. Chem., 152, 153, 163 (1972), JV
Crivello er al. J. Polymer Sci., Polymer Chem. E
d., 17, 3845 (1979), U.S. Patent No. 3,849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-16482
No. 4, JP-A-62-69263, JP-A-63-1460387, JP-A-63
Compounds described in JP-A-163452, JP-A-62-153853 and JP-A-63-146029 can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedr on Lett., (47) 4
555 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970); U.S. Patent No. 3,779,778; European Patent No.
Compounds that generate an acid by light described in JP-A-126,712 and the like can also be used. Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those that are particularly effectively used are described below. (1) The following general formula (VIII) substituted by a trihalomethyl group
Or an S-triazine derivative represented by the following general formula (IX).

[0041]

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[0042]

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In the formula, R ¹ is a substituted or unsubstituted aryl or alkenyl group, and R ² is a substituted or unsubstituted aryl, alkenyl, alkyl or —CY.
Represents ₃ . Y represents a chlorine atom or a bromine atom. The oxazole derivative (VIII) and the S-triazine derivative (I
Specific examples of X) include the following VIII-1 to VIII and compound I
X-1 to 10, but are not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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(2) An iodonium salt represented by the following general formula (X) or a sulfonium salt represented by the following general formula (XI).

[0050]

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[0051]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group,
Examples include an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom. R ³ , R ⁴ and R
⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group or a halogen atom for the aryl group, and a carbon atom for the alkyl group. 1 to 8 alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. Z ^- represents a counter anion, for example BF ₄ ^-, AsF _{6
^{-, PF 6 -, SbF 6}} -, SiF 6 -, ClO 4 -, CF 3 SO 3 -, BPh 4
^- , (Ph = phenyl), condensed polynuclear aromatic sulfonic acid anions such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dyes, etc., but are not limited thereto. Absent.

Further, two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent. The onium salts represented by the general formulas (X) and (XI) are known and described, for example, in JW Knapczyk et al.
al, J. Am. Chem. Soc., 91, 145 (1969), AL Mayc
ok et al, J. Org.Chem., 35, 2532 (1970), E. Goeth
as etal, Bull. Soc. Chem. Belg., 73, 546, (1964),
HM Leicester, J. Am. Chem. Soc., 51, 3587 (192
9), JB Crivello etal, J. Polym. Chem. Ed., 18,
2677 (1980); U.S. Pat.Nos. 2,807,648 and 4,247,47
No. 3, JP-A-53-101,331, or the method described in the gazette. Specific examples of the onium compounds of the general formulas (X) and (XI) include the following compounds X-1 to 22 and XI-1 to 34,
It is not limited to this.

[0054]

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[0055]

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[0059]

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[0060]

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[0065]

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(3) Disulfone derivatives represented by the following general formula (XII) or iminosulfonate derivatives represented by the following general formula (XIII).

[0071]

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[0072]

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Where Ar^ThreeAnd Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ⁶Is replaced or not
Represents a substituted alkyl group or an aryl group. A is a substitution
Or unsubstituted alkylene, alkenyl, or aryl
Represents a len group. Formulas represented by general formulas (XII) and (XIII)
Specific examples of the compound include compounds XII-1 to 1 shown below.
2 and XIII-1 to 12, but are not limited thereto.
Not something.

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[0075]

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[0079]

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[0080]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually in the range of 0.001 to 40% by weight based on the total solid content of the photosensitive composition. Preferably, it is used in the range of 0.1 to 20% by weight.

The positive photosensitive composition of the present invention may contain, if necessary, a compound (sensitizer) for increasing the photoacid generation efficiency of the acid-generating compound, a dye, a pigment, a plasticizer, Various known compounds can be used for the purpose of adjusting the solubility of the photosensitive composition in an aqueous alkaline solution. As the sensitizer, an electron donating compound such as pyrene or perylene, a merocyanine dye, a cyanine dye, or the like can be used, but is not limited thereto. The ratio between these sensitizers and the component (b) is preferably in the range of 0.01 / 1 to 20/1 in molar ratio and 0.1 / 1 to 5/1 in weight ratio. Further, a dye can be used as a colorant in the positive photosensitive composition of the present invention, and preferable dyes include oil-soluble dyes and basic dyes. In particular,
For example, Oil Yellow # 101, Oil Yellow # 13
0, oil pink # 312, oil green BG, oil blue BOS, oil black BY, oil black BS, oil black T-505 (all manufactured by Oriental Chemical Industry Co., Ltd.), crystal violet (CI42)
555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like.

These dyes can be added to the photosensitive composition in an amount of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total solid content of the photosensitive composition. . As the compound for adjusting the solubility of the positive photosensitive composition of the present invention in an aqueous alkaline solution, a cyclic acid anhydride, other fillers, and the like can be added. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-tetrahydrophthalic anhydride, and tetrachlorophthalic anhydride as described in U.S. Pat. No. 4,115,128. Acid, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing these cyclic acid anhydrides preferably in an amount of 1 to 15% by weight based on the total solid content of the photosensitive composition, the sensitivity can be increased up to about three times. Further, for the purpose of obtaining a difference in solubility between exposed portions and unexposed portions, for example, JP-A-62-27829, JP-A-63-250542,
JP-A-63-139343, Japanese Patent Application No. 2-177031.
No., Japanese Patent Application No. 2-138150, Japanese Patent Application No. 181-111
No. 51, Japanese Patent Application No. 59-45439, JP-A-63-13
9343, JP-A-48-39003, JP-A-51-
No. 120714, JP-A-53-133429, JP-A-55-126236, JP-A-1-106038, JP-A-64-57258 and the like. Compounds that become soluble can be used.

When the positive photosensitive composition of the present invention is used as a material for a lithographic printing plate, the composition is dissolved in a solvent that dissolves the above-mentioned components, and coated on a support. For resist materials such as semiconductors, they are used as dissolved in a solvent. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy- 2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, acetic acid Ethyl, dioxane and the like are used, and these solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 2 to 50% by weight. In addition, when used by coating, the amount of coating varies depending on the application, but, for example, when it comes to photosensitive lithographic printing plates, in general, the solid content is 0.5 to 3.0.
0 g / m ^2, also 0.1 to 3.0 g / m ² is preferred as generally solids As for the photoresist. As the coating amount decreases, the photosensitivity increases, but the film characteristics of the photosensitive film deteriorate.

When a lithographic printing plate is produced using the positive photosensitive composition of the present invention, the support may be, for example,
Paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), eg, metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., eg, cellulose diacetate, cellulose triacetate, cellulose propionate A plastic film such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc .; a metal laminated or vapor-deposited paper as described above; or a plastic film. included. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Furthermore, Japanese Patent Publication No. 48-18
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-327-327 is also preferable. Mechanical methods such as brush brushing, ball graining, liquid honing, buff graining, etc., HF, AlCl ₃ ,
After graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these roughening methods, acid or acid It is preferable that the aluminum film is etched with an alkali and then subjected to anodization in a sulfuric acid, phosphoric acid, chromic acid, sulfamic acid or a mixed acid thereof with a DC or AC power supply to provide a strong passivation film on the aluminum surface. Further, after graining treatment and anodic oxidation, sealing treatment is preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

Although the aluminum surface is hydrophilized by such a passivation film itself, if necessary, US Pat.
No. 714,066 and U.S. Pat. No. 3,181,461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat. No. 2,946,638, potassium fluoride zirconate treatment, U.S. Pat. 3,201,
No. 247, phosphomolybdate treatment, British Patent 1,108,559, alkyl titanate treatment, German Patent 1,091,443, polyacrylic acid treatment, German Patent No. 1,134,
No. 093 and British Patent No. 1,230,447, polyvinyl phosphonic acid treatment, JP-B-44-64.
No. 09, No. 3,307,951, phytic acid treatment described in JP-A-58-16893 and JP-A-58-1629.
Japanese Patent Application Laid-Open No. Sho.
Those which have been subjected to a hydrophilization treatment with an undercoat of a water-soluble polymer having a sulfonic acid group described in JP-A-9-101651 are particularly preferable. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can be exemplified.

The positive photosensitive composition of the present invention is coated on the above-mentioned support by a known coating technique. Examples of the coating technique include a spin coating method, a wire bar coating method, a dip coating method, an air knife coating method, a roll coating method, a blade coating method, a curtain coating method, and a spray coating method. The layer of the positive photosensitive composition applied as described above has a temperature of 40 to 150 ° C. for 30 seconds to 10 seconds.
It is dried using a hot air drier, an infrared drier or the like for minutes. The crosslinking between the component (a) and the component (b) includes a method of applying heat during application and drying of the photosensitive composition or a method of applying heat after coating and drying. Heating is preferably 60 ° C
Above, more preferably at 80 ° C. or more, for 30 seconds or more, preferably for 2 minutes or more. When the positive photosensitive composition of the present invention is used as a photoresist, substrates of various materials such as a copper plate or a copper plated plate, a silicon plate, a stainless steel plate, and a glass plate can be used as a support.

The photosensitive lithographic printing plate or photoresist containing the positive photosensitive composition of the present invention is usually subjected to image exposure and development steps. Examples of the light source of the actinic ray used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays. As a light source for the photoresist, g-line, i-line, and Deep-UV light are preferably used. Scanning exposure using a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium-neon laser, an argon laser, a krypton ion laser, a helium-cadmium laser, a KrF excimer laser, and the like. As a developer used for developing the positive photosensitive composition of the present invention, sodium silicate,
Potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate dibasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of an inorganic alkali agent such as, or an organic alkali agent such as tetraalkylammonium hydride is suitable, and the concentration thereof is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Is added to Further, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution as needed.

[0090]

The positive photosensitive composition of the present invention has high photosensitivity and can use light of a wide range of wavelengths.

[0091]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 24 and Comparative Examples 1 to 3 After immersing a 2S aluminum plate having a thickness of 0.24 mm in a 10% aqueous solution of sodium tertiary phosphate kept at 80 ° C. for 3 minutes to degrease, and graining with a nylon brush, Then, the resultant was etched with sodium aluminate for about 10 minutes and desmutted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was placed in a 20% sulfuric acid solution at a current density of 2 A / dm ² .
Anodizing was performed for minutes. Using the compounds shown in the following Table 1, 27 kinds of photosensitive solutions [A] were prepared according to the following formulation.
-1 to [A] -24 and [A ']-1 to [A']-3 were prepared. This photosensitive solution was applied on an anodized aluminum plate and dried at 100 ° C. for 10 minutes to prepare each photosensitive lithographic printing plate. All coating amounts at this time are in dry weight
It was adjusted to 1.7 g / m ² . Photosensitive liquid formulation [A] Linear polymer of Table 1 2.0 g Vinyl ether compound of Table 1 0.4 g Photoacid generator of Table 1 0.1 g Dioxane 50.0 g Methanol 15.0 g Heating of photosensitive layer by drying To confirm crosslinking, the obtained photosensitive lithographic printing plate was immersed in a solvent shown in Table 2 for 5 minutes,
After washing with water, the dissolved state of the coating film was observed. Table 2 shows the results.は indicates dissolution, △ indicates partial dissolution (film loss), and × indicates insoluble. Next, a gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layer of the resulting photosensitive lithographic printing plate, and exposure was performed for 20 seconds from a distance of 50 cm with a 2 KW high-pressure mercury lamp.
After heating the exposed photosensitive lithographic printing plate at 120 ° C. for 5 minutes, an undiluted developer solution having the following composition (Y): 80 g of water 3 g of triethanolamine 8 g of sodium t-butylnaphthalene sulfonate 8 g of 9 g of benzyl alcohol 9-fold diluted aqueous solution Immersion at 25 ° C. for 60 seconds and development, all of the photosensitive compositions of the present invention obtained clear positive images. Table 3 shows the results.

[0092]

Table 1 Photosensitive liquid Linear polymer Vinyl A Photoacid generator Ter compound Example 1 [A] -1 Methacrylic acid / 2-hydroxy II-11 X-21 Ethyl methacrylate / Methyl methacrylate = 20 / 20/60 (weight%), molecular weight Mw = 28,000 22 methacrylic acid / 2-hydroxy II-11 X-21 ethyl methacrylate / methyl methacrylate = 30/10/60 (weight%), molecular weight Mw = 2. 90,33 methacrylic acid / 2-hydroxy II-11 X-21 ethyl methacrylate / methyl methacrylate = 35/5/60 (weight%), molecular weight Mw = 27,744 acrylic acid / 2-hydroxye II-11 X-21 tyl methacrylate / benzyl methacrylate = 20/20/60 (% by weight), molecular weight Mw = 325,000 acrylic acid / 2-hydroxye II-11 X-21 tyl methacrylate / benzyl Methacrylate = 30/10/60 (weight%), molecular weight Mw = 2.9 66 acrylic acid / 2-hydroxyethyl II-11 X-21 tyl methacrylate / benzyl methacrylate = 35/5/60 (weight%), molecular weight Mw = 35,000 77 7 methacrylic acid / 2-hydroxy II-11 X-21 ethyl methacrylate / benzyl methacrylate = 20/20/60 (% by weight), molecular weight Mw = 4,288,8 itaconic acid / p- (2-hydroxyethyl II-11 X-21 tyl) styrene / acryl Methyl acid = 15/20/65 (% by weight), molecular weight Mw = 4,299 Maleic acid / p-hydroxystyrene II-11 X-21 ren / ethyl acrylate = 15/50/35 (% by weight) ), Molecular weight Mw = 320,000 10 10 Acrylic resin “Carboset XL II-11 X-21-44” manufactured by Goodrich Corporation 11 11 Acrylic resin “Carboset II-11 X-21525” manufactured by Goodrich Corporation 12 12 Acrylic resin “Carboset II-11 X-21 526” Goodrich 13 13 Methacrylic acid / 2-hydroxy II-9 X-21 ethyl methacrylate / benzyl methacrylate = 20/20/60 (weight%), molecular weight Mw = 420,000 14 14 methacrylic acid / 2-hydroxy II-35 X-21 ethyl methacrylate / Benzyl methacrylate = 20/20/60 (weight%), molecular weight Mw = 4,215,15 methacrylic acid / 2-hydroxy VII-9 XI-32 ethyl methacrylate / benzyl methacrylate = 20/20/60 (weight) %), Molecular weight Mw = 420,000 16 16 methacrylic acid / 2-hydroxy VII-11 X-21 silethyl methacrylate / benzyl methacrylate = 20/20/60 (% by weight), molecular weight Mw = 420,000 17 17 Same as above VII-3 X-22 18 18 Same as above VII-6 X-22 19 19 Same as above VII-13 VIII-3 20 20 Same as above II-11 X-22 21 21 Same as above II-11 IX-8 22 22 Same as above II-4 XII-10 23 23 Same as above II-17 XIII-12 24 24 Methacrylic acid / benzyl meth II-11 X-21 acrylate = 2 0/80 (wt%) molecular weight 28,000, 1 g and methacrylic acid / 2-hydroxyethyl methacrylate = 50/50 (wt%) molecular weight 22,000, 1 g Comparative Example 1 [A ']-1 methacrylic acid / 2-Hydroxy II-11 None Ethyl methacrylate / benzyl methacrylate = 20/20/60 (wt%), molecular weight Mw = 420,000 22 methacrylic acid / methyl methacrylate II-11 X-21 related = 40/60 ( % By weight), molecular weight Mw = 322,000 33-hydroxyethyl methacrylate II-12 X-21 rate / benzyl methacrylate = 20/80 (% by weight), molecular weight Mw = 43,000

[0093]

Table 2 Table 2 Solubility of the dried coating Y / water (1/2) methyl ethyl ketone dioxane toluene Example 1 × × × × 2 × × × × 3 × × × × 4 × × × × 5 × × × × 6 x x x x 7 x x x x 8 x x x x 9 x x x x 10 x x x x x 11 x x x x 12 x x x x 13 x x x x 14 x x x x 15 x x x x 16 × × × × 17 × × × × 18 × × × × 19 × × × × 20 × × × × 21 × × × × 22 × × × × 23 × × × × 24 × × × × Comparative Example 1 × × × × 2 ○ ○ ○ △ 3 × ○ ○ △

[0094]

Table 3 Image performance Number of gray scale steps Example 1 Sharp positive image 10 2 Sharp positive image 9 3 Sharp positive image 8 4 Sharp positive image 11 5 Sharp positive image 11 6 Sharp positive image 10 7 Sharp positive image 12 8 Sharp positive image 12 9 Sharp positive image 12 10 Sharp positive image 10 11 Sharp positive image 8 12 Sharp positive image 9 13 Sharp positive image 9 14 Sharp positive image 10 15 Sharp Clear Positive Image 10 16 Clear Positive Image 4 17 Clear Positive Image 7 18 Clear Positive Image 6 19 Clear Positive Image 4 20 Clear Positive Image 13 21 Clear Positive Image 2 22 Clear Positive Image 5 23 Clear Positive Image 7 24 Clear positive image 3 Comparative Example 1 Insoluble in both exposed and unexposed areas 2 Dissolved in exposed and unexposed areas 3 Reduced film in both exposed and unexposed areas (no image)

Examples 25 to 28 Photosensitive solution [A] -1 was coated on a 2 mm thick silicone wafer.
[A] -4, [A] -7 and [A] -16 were applied by a spinner, dried at 120 ° C. for 2 minutes, and adjusted to a dry film thickness of 1 g / m ² . The obtained resist was exposed using a reduction projection exposure apparatus (stepper) using monochromatic light having a wavelength of 436 nm, and then heated at 120 ° C. for 3 minutes. 2.4% of tetramethylammonium hydroxide
By developing with an aqueous solution for 60 seconds, a resist pattern was formed. As a result, 0 in all samples.
A good pattern of 7 μm lines and spaces was obtained. Example 29 The photosensitive lithographic printing plate obtained in Example 17 was brought into close contact with a gray scale having a density difference of 0.15 on the photosensitive layer, and was exposed to a 2 KW high-pressure mercury lamp from a distance of 50 cm for 20 seconds. After heating the exposed photosensitive lithographic printing plate at 120 ° C. for 5 minutes,
-3C (trade name: manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. for 20 seconds, 30 seconds, 1 minute,
, 5 minutes, and 10 minutes. As a result, good positive images were obtained in all cases, and the number of gray scale stages was all 13 stages. From the above results, the positive photosensitive composition of the present invention was highly sensitive and a clear positive image was obtained. Further, it was found that the developing latitude of the positive photosensitive composition was wider than that of Example 29.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-12995 (JP, A) JP-A-63-71840 (JP, A) JP-A-2-19847 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) G03F 7/039 G03F 7/00 G03F 7/004 G03F 7/038 G03F 7/38

Claims (1)

(57) [Claims] 1. A compound having at least two enol ether groups represented by the following general formula (I): (b) a linear polymer having an acid component and a hydroxyl group; and (c) an actinic ray or radiation A compound containing a compound that decomposes upon irradiation to generate an acid, is applied to a support and dried.
For positive photosensitive materials, when coating or drying
Before the post-image exposure step, the component (a) is
(B) A positive photosensitive material characterized by crosslinking the component . In the formula, R ₁ , R ₂ and R ₃ represent hydrogen, an alkyl group or an aryl group, which may be the same or different. Also, two of them may combine to form a saturated or olefinically unsaturated ring.