JP2006084634A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which is concurrently equipped with high planarization performance and high sensitivity and has high visible light transmittance, in the formation of a cured resin pattern. <P>SOLUTION: In the radiation-sensitive resin composition comprising a curable alkali-soluble resin (A), a quinonediazido compound (B) and a solvent (C), the curable alkali-soluble resin (A) is a polymer obtained by polymerization, using an azo-based radical polymerization initiator (ai) that does not have nitrile group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive resin composition, a cured resin pattern formed using the same, and a method for producing the same.

  Radiation sensitive resin compositions include, for example, TFT insulating films used in thin film transistor (hereinafter referred to as TFT) type liquid crystal display devices and organic EL display devices, and diffuse reflectors used in reflective TFT substrates. It is useful as a material for forming a cured resin pattern including an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like (see Patent Document 1). Moreover, in order to obtain a brighter display image, a high transmittance with respect to visible light is required (for example, see paragraph number 0010 of Patent Document 1).

Japanese Patent Laid-Open No. 9-152625 (see paragraph numbers 0001, 0009 and 0010)

However, the radiation-sensitive resin composition or the like has insufficient transmittance for visible light, and a radiation-sensitive resin composition having a higher transmittance is demanded.
The objective of this invention is providing the radiation sensitive resin composition which has high planarization performance, high sensitivity, etc., and has high visible light transmittance | permeability in formation of a cured resin pattern.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention relates to a radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B) and a solvent (C), wherein the curable alkali-soluble resin (A) is: A radiation-sensitive resin composition, which is a polymer obtained by polymerization using an azo radical polymerization initiator (ai) having no nitrile group, a cured resin pattern formed by the composition, And after applying the composition and removing the solvent, irradiating with radiation through a mask, and then developing with an alkaline aqueous solution to form a predetermined pattern, and then irradiating the entire pattern on the substrate with radiation. A method for producing a cured resin pattern is provided.

  The radiation-sensitive resin composition of the present invention can produce a film having a high visible light transmittance.

  The curable alkali-soluble resin (A) in the present invention includes a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group. A polymer is preferably used [provided that the unsaturated compound leading to the structural unit (a2) is not an unsaturated carboxylic acid).

  Examples of the structural unit (a1) include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acid or unsaturated dicarboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and cinnamic acid.

Examples of the structural unit (a2) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and 3-methyl-3,4-epoxybutyl (meth) acrylate. , 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 1-vinylcyclohexene oxide, 3-vinylcyclohexene oxide or 4-vinylcyclohexene oxide. Any epoxy group-containing unsaturated compound; 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-phenyl- 3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meta ) Acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2-pentafluoroethyl-3- (meth) acryloxyethyloxy Such as oxetanyl group-containing unsaturated compound such as Tan and the like.
As the structural unit (a2), the oxetanyl group-containing unsaturated compound is preferable. Preferred oxetanyl group-containing unsaturated compounds include, for example, 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl- 3- (meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryl Roxyethyl oxetane or 2-pentafluoroethyl-3- (meta Such acryloxyethyl oxetane and the like. A particularly preferred oxetanyl group-containing unsaturated compound is 3-ethyl-3-methacryloxymethyloxetane.
When the radiation sensitive resin composition is prepared using an alkali-soluble resin containing an unsaturated compound containing an oxetanyl group as the structural unit (a2), the storage stability of the composition tends to be good. ,preferable.

  In the present invention, the curable alkali-soluble resin (A) further comprises a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond as a copolymer component, and polymerizable carbon-carbon unsaturation. At least one selected from the group consisting of a structural unit (a32) derived from an aromatic compound having a bond, a structural unit (a33) derived from a vinyl cyanide compound, and a structural unit (a34) derived from an N-substituted maleimide compound. The structural unit (a3) can be included.

Examples of the carboxylic acid ester having an olefinic double bond that leads to the structural unit (a31) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , Unsaturated carboxylic acids such as benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate Acid esters;
Unsaturated alkyl carboxylic acid aminoalkyl esters such as aminoethyl (meth) acrylate;
Examples include structural units derived from carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate.

  Examples of the aromatic compound having a polymerizable carbon-carbon unsaturated bond that leads to the structural unit (a32) include styrene, α-methylstyrene, vinyltoluene, and the like.

  Examples of the vinyl cyanide compound from which the structural unit (a33) is derived include a structural unit derived from a vinyl cyanide compound such as acrylonitrile, methacrylonitrile, or α-chloro (meth) acrylonitrile.

  Examples of the N-substituted maleimide compound that leads to the structural unit (a34) include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- ( 4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3 -Maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2-benz Oxazolyl) phenyl] maleimide, N- ( - acridinyl) maleimide and the like.

  The structural units (a1), (a2), (a31), (a32), (a33), and (a34) can be used as a single unit or a combination of units derived from the exemplified compounds.

In the copolymer containing the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having the curable group, the structural ratio of the structural unit (a1) is: Preferably it is 5-50 mol% with respect to the total mole number of the structural unit of a polymer, More preferably, it is 15-40 mol%. Moreover, the structural ratio of the structural unit (a2) is preferably 5 to 95 mol%, more preferably 15 to 85 mol%, based on the total number of moles of the structural units of the copolymer.
In the composition of the present invention, it is preferable that the constituent ratios of the structural units (a1) and (a2) in the copolymer are in the above ranges from the viewpoint of an appropriate dissolution rate in the developer and high curability.

  In the composition of the present invention, when the alkali-soluble resin (A) contains other structural unit (a3) as an optional component in addition to the structural units (a1) and (a2), the structural ratio of (a3) The molar fraction is preferably 0.01 to 90 mol%, more preferably 0.01 to 80 mol%, based on the total number of moles of all structural units constituting the coalescence.

  As a method for obtaining a copolymer having the above structural unit, a radical polymerization method is usually used. In the synthesis of the resin used in the present invention, an azo radical polymerization initiator having no nitrile group is used. Examples of the azo radical polymerization initiator having no nitrile group include compounds represented by the formula (1).

In Expression ^(1), R 1 ~R ⁴ each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms.
A ¹ and A ² are each independently an optionally substituted alkyl group having 1 to 6 carbon atoms, a substituent represented by formula (2), or a substituent represented by formula (3). Represents.

In formula (2) and formula (3), X ¹ and X ² each independently represent a group or atom selected from the group consisting of NR ⁷ , O and S.
Y ¹ and Y ² each independently represent a single bond or a group or atom selected from the group consisting of N (R ⁸ ), O and S.
R ⁵ , R ⁶ and R ⁸ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
R ⁷ represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ]

Specific examples of R ^{1 to} R ⁶ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a tert-butyl group. N-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, cyclopentyl group, n -Hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2- Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, cyclo Examples include hexyl group, cyclopentylmethyl group, methylcyclohexyl group, methoxymethyl group, methoxyethyl group, methoxypropyl, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl, ethoxybutyl group, and phenyl group, preferably A hydrocarbon group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, or a phenyl group; More preferably, a methyl group, an ethyl group, or a phenyl group is mentioned.

R ⁷ includes a hydroxyl group in addition to those exemplified as specific examples of R ^{1 to} R ⁶ and R ⁸ above.

Specific examples of the substituent represented by the formula (2) include ester groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group;
Carboxyl group;
Amide groups such as amide group, dimethylamide group, diethylamide group, butyramide group, cyclohexylamide group, hydroxyethylamide group;
Amidino groups such as amidino group, dimethylamidino group, carboxyethylamidino group, 2-imidazolinyl group, methylimidazolinyl group, hydroxyethylimidazolinyl group, 2-tetrahydropyrimidyl group;
Amidoxime groups such as amidoxime group and dimethylamidoxime group;
A thiocarboxyl group;
Dithiocarboxyl group;
Methoxythiocarbonyl group, ethoxythiocarbonyl group, propoxythiocarbonyl group, butoxythiocarbonyl group, methylthiocarbonyl group, ethylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, methyldithiocarbonyl group, ethyldithiocarbonyl group, Thioester groups such as propyldithiocarbonyl group and butyldithiocarbonyl group;
And thioamide groups such as thioamide and dimethylthioamide.

Specific examples of the substituent represented by the formula (3) include ester groups such as formyloxy group, acetoxy group, propionyloxy group, butyryloxy group;
Amido groups such as formamide group, N-methylformamide group, N-ethylformamide group, acetamide group, N-methylacetamide group, N-ethylacetamide group;
Amidino groups such as formylamidino group, N-methylformamidino group, acetamidino group, N-methylacetamidino group;
Thioester groups such as thioformyloxy group, thioacetoxy group, thiopropionyloxy group, thiobutyryloxy group, etc .;
And thioamide groups such as thioformamide and thioacetamide.

Specific examples of A ¹ and A ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, cyclopentyl group, n-hexyl group 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl Group, cyclopentylmethyl group, methylcyclohexyl group, a hydrocarbon group such having 1 to 6 carbon atoms such as a phenyl group;
Alkoxyalkyl groups having 1 to 6 carbon atoms such as methoxymethyl group, methoxyethyl group, methoxypropyl, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl, ethoxybutyl group;
Ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group;
Carboxyl group;
Amide groups such as amide group, dimethylamide group, diethylamide group, butyramide group, cyclohexylamide group, hydroxyethylamide group;
Amidino groups such as amidino group, dimethylamidino group, carboxyethylamidino group, 2-imidazolinyl group, methylimidazolinyl group, hydroxyethylimidazolinyl group, 2-tetrahydropyrimidyl group;
Amidoxime groups such as amidoxime group and dimethylamidoxime group;
A thiocarboxyl group;
Dithiocarboxyl group;
Methoxythiocarbonyl group, ethoxythiocarbonyl group, propoxythiocarbonyl group, butoxythiocarbonyl group, methylthiocarbonyl group, ethylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, methyldithiocarbonyl group, ethyldithiocarbonyl group, Thioester groups such as propyldithiocarbonyl group and butyldithiocarbonyl group;
And thioamide groups such as thioamide and dimethylthioamide. Preferably, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 2- Methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, cyclopentylmethyl Group, methylcyclohexyl group, a hydrocarbon group such having 1 to 6 carbon atoms such as a phenyl group;
Alkoxyalkyl groups having 1 to 6 carbon atoms such as methoxymethyl group, methoxyethyl group, methoxypropyl, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl, ethoxybutyl group;
Examples thereof include esters such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group.

As the azo radical polymerization initiator having no nitrile group represented by the formula (1), specifically, azo-tert-octane, azo-tert-butane, dimethyl 2,2′-azobisisobutyrate, 2, Diethyl 2′-azobisisobutyrate, dipropyl 2,2′-azobisisobutyrate, dibutyl 2,2′-azobisisobutyrate, 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (isobutyl) Amide), 2,2′-azobis {(N-butyl) isobutyramide}, 2,2′-azobis {(N-cyclohexyl) isobutyramide}, 2,2′-azobis {(N-hydroxyethyl) isobutyramide }, 2,2′-azobis [N- {2- (1-hydroxybutyl)} isobutyramide], 2,2′-azobis [N- {1,1-bis (1-hydride) Chimethyl) -2-hydroxyethyl} isobutyramide], 2,2′-azobis (2-amidinopropane), 2,2′-azobis [2- {N- (2-carboxyethyl) amidino} propane], 2, 2′-azobis {2- (2-imidazolin-2-yl) propane}, 2,2′-azobis {2- (5-methyl-2-imidazolin-2-yl) propane}, 2,2′-azobis {2- (3,4,5,6 tetrahydropyrimidin-2-yl) propane}, 2,2′-azobis (2-methylpropionamidoxime), 2,2′-azobis (2-methylbutaneamidoxime) and the like Preferably, azodi-tert-octane, azodi-tert-butane, 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobisisobutyric acid dimethy , 2,2′-azobisisobutyric acid diethyl, and 2,2′-azobisisobutyric acid dipropyl, and more preferably dimethyl 2,2′-azobisisobutyrate and diethyl 2,2′-azobisisobutyrate.
The azo radical polymerization initiator having no nitrile group may be used alone or in combination.

  The amount of the azo radical polymerization initiator having no nitrile group can be appropriately selected as long as smooth copolymerization is not impaired, and constitutes the curable alkali-soluble resin (A) used in the present invention. The mass fraction is preferably 1 to 10% by mass and more preferably 2 to 8% by mass with respect to the total amount of the compound for deriving the structural unit to be synthesized and the azo radical polymerization initiator.

  In addition, a known chain transfer agent may be used to adjust the molecular weight of the polymer. Examples of the chain transfer agent include alkyl mercaptans, alkyl sulfides, alkyl disulfides, thioglycolic acid esters, α-methylstyrene dimers, and the like.

Examples of the method for producing a copolymer having the above structural unit include the following methods.
(1) As described in J. Polym. Sci., Polym. Chem. (1968), 6 (2), 257-267, a monomer and a polymerization initiator are mixed in an organic solvent, and further if necessary. , A method in which a chain transfer agent is mixed and solution polymerization is performed at about 60 to 300 ° C .;
(2) Suspension at about 60 to 300 ° C. using a solvent in which the monomer does not dissolve, as described in J. Polym. Sci., Polym. Chem. (1983), 21 (10), 2949-2960 Polymerization or emulsion polymerization;
(3) a method of bulk polymerization at 60 to 200 ° C. as described in JP-A-6-80735;
(4) As described in JP-A No. 10-195111, the monomers to be used are continuously supplied to the polymerization vessel, and in the polymerization vessel at 180 to 300 ° C. in the presence or absence of the polymerization initiator. A method of heating for 5 to 60 minutes and continuously removing the resulting reaction product from the polymerization vessel.

Among them, a method in which a monomer and a polymerization initiator are mixed and reacted in an organic solvent, a method in which a monomer is continuously fed into an organic solvent to which a polymerization initiator is added, a monomer and a polymerization initiator are mixed in an organic solvent A continuous feed method is advantageous. In order to disperse the reaction heat, a method of continuously supplying the monomer is preferable. Further, in order to obtain a polymer compound having a narrow molecular weight distribution, a method of continuously supplying a polymerization initiator is preferable.
The reaction is preferably performed at 40 to 200 ° C, more preferably 50 to 150 ° C, particularly preferably 60 to 120 ° C, preferably 1 to 20 hours, more preferably 2 to 10 hours. When supplying a monomer continuously, the method of continuing heating for 1 to 10 hours after supplying the whole quantity over 1 to 5 hours is also preferable. The reaction concentration is preferably 10 to 70%, more preferably 20 to 60%, in terms of mass% of the total monomers with respect to the total reaction solution.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and cyclohexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone;
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tetraethyl Glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1 -Ethers such as butanol;
Ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, 1,3-propanediol diacetate, ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, methyl 2-hydroxyisobutanoate, ethylene carbonate, propylene Carbonates, esters such as butyrolactone;
Aromatic hydrocarbons such as toluene and xylene are exemplified.
Two or more organic solvents may be used as the organic solvent.

  Examples of the copolymer containing the structural units (a1) and (a2) include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / Benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl-3- Methacryloxymethyl Xetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / benzyl Acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl acrylate copolymer, 3-ethyl -3-methacryloxymethyl oxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer, or 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl acrylate copolymer, 3-ethyl-3-meth Methacryloxy methyl oxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloxy oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

  The weight average molecular weight determined by gel permeation chromatography based on the polystyrene of the copolymer containing the structural units (a1) and (a2) is preferably 2,000 to 100,000, more preferably 2,000. 50,000 to 50,000, particularly preferably 3,000 to 20,000. When the weight average molecular weight is in the above range, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.

  Content of the copolymer containing the structural units (a1) and (a2) in the radiation sensitive resin composition of this invention is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 50- It is 98 mass%, More preferably, it is 60-95 mass%.

  Examples of the quinonediazide compound (B) in the radiation-sensitive resin composition of the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, 1,2-naphthoquinonediazide sulfonic acid amide and the like.

  Specific examples of the quinonediazide compound (B) include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide. -5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones such as acid esters; 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2,2 ′ , 4,4'-Tetrahydroxybenzofe Non-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,3 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4 , 4′-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 , 4,2'-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,4′-tetrahydroxy-3′- 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as methoxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester; 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1, 1,2- of pentahydroxybenzophenones such as 2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Naphthoquinone diazide sulfonate; 2, , 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 3,4,5,3 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) Methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydride) Roxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p- Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3 , 4-Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfone Ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) ) Propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4- Sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide- -Sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) ) -2-Hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ', 6', 7'-Hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7 , 5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyl Laban-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester ( Polyhydroxyphenyl) alkanes such as 1,2-naphthoquinonediazide sulfonic acid ester.

  The quinonediazide compound (B) is used alone or in combination of two or more. Content of the quinonediazide compound (B) in this invention becomes like this. Preferably it is 2-50 mass% with respect to the total solid of a radiation sensitive resin composition, More preferably, it is 5-40 mass%. When the content of the quinonediazide compound is within the above range, the difference in dissolution rate between the unexposed area and the exposed area tends to be high, and thus there is a tendency that the developed residual film ratio tends to be kept high.

The radiation sensitive resin composition of this invention contains a solvent (C). As a solvent (C), the organic solvent generally used for a radiation sensitive resin composition can be used.
Examples of such organic solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether or diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether and diethylene glycol ethyl methyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate or ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol Propylene glycol alkyl ether acetates such as monoethyl ether acetate or propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; aromatic hydrocarbons such as benzene, toluene or xylene; methyl ethyl ketone, Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerol; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-hydroxyisobutanoic acid methyl, ethyl lactate, butyl lactate, acetate Le, amyl acetate or methyl pyruvate, and esters such as 1,3-butanediol diacetate.

  Content of the said solvent (C) is a mass fraction with respect to the radiation sensitive resin composition whole quantity, Preferably it is 50-95 mass%, More preferably, it is 70-90 mass%. When the content of the solvent (C) is in the above range, a film having good flatness tends to be formed, which is preferable.

  In addition to the alkali-soluble resin (A), the quinonediazide compound (B) and the solvent (C), the radiation-sensitive resin composition of the present invention comprises a cationic polymerization initiator (D), a polyhydric phenol compound (E), a crosslinking agent ( F), a polymerizable monomer (G), a silane coupling agent (H) and a surfactant (I) may be contained.

Examples of the cationic polymerization initiator (D) include onium salts having cationic polymerization initiating ability. The onium salt is composed of an onium cation and an anion derived from a Lewis acid.
Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p- Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (pt-butylphenyl) sulfonium, tris (p-cyanophenyl) Sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, dimethyl ( Isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) Sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyloxy) sulfur Chloride, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.
Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, triphenylsulfonium or tris (pt-butylphenyl). ) Sulfonium and the like.
Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroalcinate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic polymerization initiator (D) include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (pt-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl). ) Iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxy) Phenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethyl naphthyl sulfoni Muhexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate , Dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (t-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluoro Lophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium Hexafluorophosphate, diphenyliodonium hexafluoro Lucinate, bis (p-tolyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, bis (p-octylphenyl) iodonium hexafluoroalcinate, bis (p-octadecylphenyl) iodonium Hexafluoroarsinate, bis (p-octyloxyphenyl) iodonium hexafluoroarsinate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsinate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroalcinate, (p- Tolyl) (p-isopropylphenyl) iodonium hexafluoroarsinate, methyl naphthyl iodonium hexafluoroarsinate, ethyl naphthyl Donium hexafluoroarsinate, triphenylsulfonium hexafluoroarsinate, tris (p-tolyl) sulfonium hexafluoroarsinate, tris (p-isopropylphenyl) sulfonium hexafluoroarsinate, tris (2,6-dimethylphenyl) Sulfonium hexafluoroarsinate, tris (p-t-butylphenyl) sulfonium hexafluoroarsinate, tris (p-cyanophenyl) sulfonium hexafluoroalcinate, tris (p-chlorophenyl) sulfonium hexafluoroalcinate, dimethylnaphthylsulfonium hexa Fluoroalcinate, diethylnaphthylsulfonium hexafluoroarsinate, dimethyl (methoxy) sulfonium hexafluoroa Lucinate, dimethyl (ethoxy) sulfonium hexafluoroarsinate, dimethyl (propoxy) sulfonium hexafluoroarsinate, dimethyl (butoxy) sulfonium hexafluoroarsinate, dimethyl (octyloxy) sulfonium hexafluoroarsinate, dimethyl (octadecanoxy) sulfonium hexa Fluoroalcinate, dimethyl (isopropoxy) sulfonium hexafluoroalcinate, dimethyl (t-butoxy) sulfonium hexafluoroalcinate, dimethyl (cyclopentyloxy) sulfonium hexafluoroalcinate, dimethyl (cyclohexyloxy) sulfonium hexafluoroalcinate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsine , Dimethyl (2-chloroethoxy) sulfonium hexafluoroarsinate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsinate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsinate, dimethyl (8-nitrooctyloxy) sulfonium Hexafluoroalcinate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroalcinate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroalcinate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroalcinate, Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bi (Pt-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p-octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexa Fluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl Naphthyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfo Nium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p- t-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate , Dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfate Nium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl ( Isopropoxy) sulfonium hexafluoroantimonate, dimethyl (t-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexanium Fluoroantimonate, dimethyl ( -Chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, Dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate, diphenyliodonium tetrakis (penta Fluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentaph Fluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluoro) Phenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (penta) Fluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethyl naphthyl iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, Tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, (P-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) ) Borate, dimethyl (octadecanoxy) sulfoni Um tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (t-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) Borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3- Bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-Cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate Dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate, etc., preferably bis (p-tolyl) iodonium hexa Fluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (pt-t- Tilphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsinate, (p-tolyl) (p-isopropylphenyl) ) Iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroarsinate, tris (pt-butylphenyl) sulfonium hexafluoroalcinate, bis (p-tolyl) ) Iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p- (t-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) And sulfonium tetrakis (pentafluorophenyl) borate, and more preferably bis (p-tolyl) iodonium hexafluoroantimonate, ) (P-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate Bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (penta Fluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, or tris (pt-butylphenyl) sulfonium tetra Scan (pentafluorophenyl) borate.

  When using the said cationic polymerization initiator (D), the content becomes like this with respect to the total solid of a radiation sensitive resin composition, Preferably it is 0.01-10 mass%, More preferably, it is 0.1. ˜5 mass%. When the content of the polymerization initiator (D) is in the above range, by increasing the curing rate at the time of thermosetting, a decrease in resolution at the time of thermosetting is suppressed, and the solvent resistance of the cured film is further improved. Is preferable.

Examples of the polyhydric phenol compound (E) include a compound having two or more phenolic hydroxyl groups in the molecule, a polymer obtained using at least hydroxystyrene as a raw material monomer, or a novolak resin.
Examples of the compound having two or more phenolic hydroxyl groups in the molecule include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, or (polyhydroxy) exemplified in the description of the quinonediazide compound. And the same polyhydric phenols as phenyl) alkanes.

Specific examples of the polymer obtained using at least hydroxystyrene as a raw material monomer include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer or hydroxy Examples thereof include resins obtained by polymerizing hydroxystyrene such as styrene / alkoxystyrene copolymers.
Further, the novolak resin may be, for example, one or more compounds selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones. Examples thereof include resins obtained by polymerization.

  When using the said polyhydric phenol compound (E), the usage-amount is preferably 0.01 mass% or more and 40 mass% or less with respect to the total solid of a radiation sensitive resin composition, More preferably, it is 0.1. It is 1 mass% or more and 25 mass% or less. When the content of the polyhydric phenol compound (E) is in the above range, the resolution is improved and the visible light transmittance tends not to decrease, which is preferable.

  Examples of the crosslinking agent (F) include methylol compounds.

  Examples of the methylol compound include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins. Here, examples of the alkoxymethylated melamine resin include a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin, and a butoxymethylated melamine resin. Examples of the alkoxymethylated urea resin include methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, and butoxymethylated urea resin. The above crosslinking agents can be used alone or in combination of two or more.

  In the radiation sensitive resin composition of this invention, when using a crosslinking agent (F), the usage-amount is preferably 0.01 mass% or more and 15 mass% with respect to the total solid of a radiation sensitive resin composition. It is as follows. When the content of the crosslinking agent is in the above range, the visible light transmittance of the obtained film is increased, and the performance as the cured resin pattern is improved, which is preferable.

  Examples of the polymerizable monomer (G) include a polymerizable monomer that can be radically polymerized by heating or a polymerizable monomer that can be cationically polymerized. A preferable polymerizable monomer (G) includes a polymerizable monomer capable of cationic polymerization.

  Examples of the polymerizable monomer capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond. The compound having a polymerizable carbon-carbon unsaturated bond may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, or a polyfunctional (trifunctional or higher functional) polymerizable monomer. There may be.

  Examples of the monofunctional polymerizable monomer include nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-ethylhexyl carbitol acrylate, Examples include 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or N-vinyl pyrrolidone.

  Examples of the bifunctional polymerizable monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol dimethacrylate. , Triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like.

Examples of the tri- or higher functional polymerizable monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, penta Examples include erythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.
Among the compounds having a polymerizable carbon-carbon unsaturated bond, a bifunctional or polyfunctional polymerizable monomer is preferably used. Specifically, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate is preferable, and dipentaerythritol hexaacrylate is more preferable. Further, a bifunctional or polyfunctional polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.

Examples of the polymerizable monomer capable of cationic polymerization include monomers having a cationic polymerizable functional group such as vinyl ether group, propenyl ether group, epoxy group or oxetanyl group.
Examples of the monomer containing a vinyl ether group include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, and dodecyl vinyl ether.
Examples of the monomer containing the propenyl ether group include 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one.
Examples of the compound containing an epoxy group include a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a heterocyclic type. An epoxy resin etc. are mentioned.
Examples of the compound containing the oxetanyl group include bis {3- (3-ethyloxetanyl) methyl} ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, and 1,3-bis { 3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis {3- (3-ethyloxetanyl) methoxymethyl} benzene, 1,3-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1 , 4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,3-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,4-bis {3- (3-ethyloxetanyl) methoxy Methyl} cyclohexane, 1,3-bis {3- (3-ethyloxetanyl) methoxymethyl} cyclohexane or 3- And 3 ethyloxetanyl) methyl novolak resins.

The said polymerizable monomer (G) is used individually or in combination of 2 or more types.
When the polymerizable monomer (G) in the radiation sensitive resin composition of the present invention is used, the amount used is a mass fraction with respect to the total solid content of the radiation sensitive resin composition, preferably 20% by mass or more. % Or less, more preferably 0.01 mass% or more and 10 mass% or less.

Examples of the silane coupling agent (H) include methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyltris (2-methoxyethoxy). Silane, 3-chloropropyl-trimethoxysilane, 3-chloropropylmethyl-dichlorosilane, 3-chloropropylmethyl-dimethoxysilane, 3-chloropropylmethyl-diethoxysilane, 3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-methacryloyloxypropyl-trimethoxysilane, 3-meta Liloyloxypropylmethyl-dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, N-2- (N-vinylbenzylaminoethyl) -3-aminopropyl-trimethoxysilane hydrochloride, hexamethyl Disilazane, diaminosilane, triaminopropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropylmethyl-diethoxysilane, 3-aminopropyl-tris (2 -Methoxyethoxyethoxy) silane, 3- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -3-aminopropylmethyl-dimethoxysilane, 3-ureidopropyl-trimethoxy Silane, 3-ureidop Pill-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropylmethyl-dimethoxysilane, N-methyl-3-aminopropyl-trimethoxysilane, N-phenyl -3-aminopropyl-trimethoxysilane and the like, preferably 3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, 2 Examples include silane coupling agents having an epoxy group such as-(3,4-epoxycyclohexyl) ethyl-trimethoxysilane, more preferably alicyclic rings such as 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane. Silane coupling agents having an epoxy group I can get lost.
When using a silane coupling agent (H), the usage-amount is a mass fraction with respect to a radiation sensitive resin composition, Preferably it is 0.01-10 mass%, More preferably, it is 0.1-2. It is mass%, Most preferably, it is 0.2-1 mass%. When the amount of the silane coupling agent is within the above range, the adhesiveness between the cured resin pattern and the substrate is improved when the cured resin pattern is formed using the radiation-sensitive resin composition of the present invention. There is a tendency and preferable.

The surfactant (I) preferably contains at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. .
Examples of the silicone-based surfactants include trade names such as Torresilicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, and SH30PA (produced by Torresilicone); trade name polyether-modified silicone oil SH8400 (Trade name KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone)); trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 , TSF4452 and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

Examples of the fluorosurfactant include Fluorard FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); MegaFac (trade name) F142D, F171, F172, F173, F177, F183, and R183 (trade name). Dainippon Ink & Chemicals, Inc.); Ftop (trade name) EF301, EF303, EF351 and EF352 (made by Shin-Akita Kasei Co., Ltd.);
Surflon (trade name) S381, S382, SC101 and SC105 (Asahi Glass Co., Ltd.);
Product names E1830, E5844 (Daikin Fine Chemical Laboratory Co., Ltd.);
Product names BM-1000, BM-1100 (manufactured by BM Chemie) and the like can be mentioned.
Examples of the silicone surfactant having a fluorine atom include Megafac (trade name) R08, BL20, F475, F477 and F443 (Dainippon Ink Chemical Co., Ltd.).
These surfactants can be used alone or in combination of two or more.

Furthermore, you may use together other surfactants, such as an acrylic polymer type surfactant and a vinyl polymer type surfactant, in the curable resin composition of this invention.
Examples of the acrylic polymer surfactant include Disparon (trade name) OX-880, OX-881, OX-883, OX-70, OX-77, OX-77HF, OX-60, and OX-60. OX-710, OX-720, OX-740, OX-750, OX-8040, 1970, 230, L-1980-50, L-1982-50, L-1983-50 L-1984-50, L-1985-50, LAP-10, LAP-20, LAP-30 and LHP-95 (manufactured by Enomoto Kasei Co., Ltd.); trade names BYK-352, BYK -354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 and BYK-390 (manufactured by BYK Chemie Japan); Efcar (trade name) LP3 78 (Efka Chemicals Co., Ltd.), and the like.

  Examples of the vinyl polymer surfactant include Disparon (trade name) 1922, 1927, 1950, 1951, P-410, P-410HF, P-420, P-425, and PD-7. And LHP-90 (manufactured by Enomoto Kasei Co., Ltd.).

  The radiation-sensitive resin composition of the present invention may contain other components as necessary, for example, an antioxidant, a dissolution inhibitor, a sensitizer, an ultraviolet absorber, a light stabilizer, an adhesion improver, or an electron donor. Various additives such as can also be contained.

  The radiation sensitive resin composition of the present invention is prepared by, for example, mixing a solution obtained by dissolving the alkali-soluble resin (A) in the solvent (C) and a solution obtained by dissolving the quinonediazide compound (B) in the solvent (C). Can be prepared. Moreover, you may add and mix a solvent (C) to the liquid after preparation. Furthermore, it is preferable to remove solids by filtration after mixing the solutions. The filtration is preferably performed using a filter having a pore size of 3 μm or less (preferably about 0.1 to 2 μm). The solvent (C) used for the alkali-soluble resin (A) and the quinonediazide compound (B) may be the same as each other. A plurality of solvents (C) may be used as long as they are compatible with each other.

  When forming a cured resin pattern using the radiation-sensitive resin composition of the present invention, for example, a layer (1) made of the radiation-sensitive resin composition is formed on a substrate (2) [FIG. a)], and after exposing the layer (1) to the radiation (4) through the mask (3) [see FIG. 1 (b)], development may be performed (see FIG. 1 (c)). ].

  Examples of the substrate (2) include a transparent glass plate. Circuits such as TFTs and CCDs, color filters, and the like may be formed on the substrate.

  The layer (1) comprising the radiation sensitive resin composition can be formed by, for example, a method of applying the radiation sensitive resin composition on the substrate (2). The coating is performed by, for example, spin coating, casting coating method, roll coating method, slit and spin coating, slit coating method, die coating method, curtain flow coating method and the like. After application, the radiation-sensitive resin composition layer (1) is formed by heat-drying (pre-baking) or vacuum-drying after heating to volatilize volatile components such as a solvent. The physical layer (1) contains almost no volatile components. Moreover, the thickness of the said radiation sensitive resin composition layer is about 1.5-5 micrometers.

  Thereafter, the radiation-sensitive resin composition layer (1) is irradiated with radiation (4) through a mask (3). The pattern of the mask (3) is appropriately selected according to the target pattern of the cured resin pattern. As the radiation, for example, light rays such as g-line or i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown) so as to be irradiated in parallel over the entire surface of the radiation-sensitive resin composition layer. By irradiating with radiation in this way, alignment between the mask and the radiation-sensitive resin composition layer can be performed accurately.

  After the exposure, development is performed. Development can be performed on the radiation-sensitive resin composition layer (1) after exposure by, for example, a paddle method, a dipping method, or a shower method. As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

  Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, Examples thereof include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. It is done.
The above alkaline compounds may be used alone or in combination of two or more. The content of the alkaline compound is a mass fraction with respect to the developing solution, and is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

  The developer may contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants.

  Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. And polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester or polyoxyethylene alkylamine.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate;
Alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate;
Examples thereof include alkylaryl sulfonates such as sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate. These surfactants may be used alone or in combination of two or more.

  Further, the developer may contain an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol and ethanol.

  Of the radiation-sensitive resin composition layer (1), the radiation-irradiated region (12) irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated region (not irradiated with radiation) ( 11) remains without dissolving in the developer to form pattern (5).

  Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time which makes a radiation sensitive resin composition layer (1) contact with a developing solution is short, a radiation irradiation area | region (12) Easily dissolves and is removed. Moreover, since it contains a quinonediazide compound (B), even if the time during which the radiation-sensitive resin composition layer (1) is brought into contact with the developer becomes long, the radiation non-irradiated region (11) dissolves in the developer and disappears. There is nothing to do.

  After alkali development, it is usually washed with water and dried. After drying, radiation is irradiated over the entire surface of the obtained transparent film pattern (5). The radiation irradiated here is preferably ultraviolet rays or deep ultraviolet rays, and the irradiation amount per unit area is usually larger than the irradiation amount in the previous exposure.

  The pattern (5) thus formed is preferably further subjected to heat treatment (post-baking). The heat treatment is performed by a method in which the substrate that has been irradiated with radiation over the entire surface is heated by a heating device such as a hot plate or a clean oven. In the heat treatment, the heating temperature is usually 150 to 250 ° C., preferably 180 to 240 ° C., and the heating time is usually 5 to 120 minutes, preferably 15 to 90 minutes. Heat treatment tends to improve the heat resistance and solvent resistance of the cured resin pattern, which is preferable.

  As mentioned above, although embodiment of this invention was described, embodiment of the said disclosed invention is an illustration to the last, Comprising: The scope of the present invention is not limited to these embodiment. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Synthesis Example 1: Resin A1
In a separable flask, 210 g of a mixed solvent of diethylene glycol ethyl methyl ether and ethyl-3-ethoxypropionate [former / latter (weight ratio) = 340/345], 120 g of N-cyclohexylmaleimide, 3-ethyl-3-oxetanylmethyl After adding 140 g of methacrylate and 40 g of methacrylic acid and replacing with nitrogen, the temperature was raised to 80 ° C. When the temperature of the contents reaches 80 ° C., a solution obtained by dissolving 15 g of dimethyl-2,2′-azobis (2-methylpropionate) as a polymerization initiator in 160 g of the mixed solvent is added over about 7 hours. It was dripped. After completion of dropping of the polymerization initiator solution, the reaction was continued for about 1 hour, and then the reaction vessel was cooled to complete the reaction. To this solution, 315 g of the mixed solvent was added to adjust the solid concentration, and about 1 kg of the mixed solvent solution of N-cyclohexylmaleimide / 3-ethyl-3-oxetanylmethyl methacrylate / methacrylic acid copolymer was obtained. The obtained copolymer solution had a solid content concentration of 28.9% by weight and an acid value of 26.5 mg-KOH / g. The polystyrene equivalent weight average molecular weight of this resin A1 was 8,300.

Here, the polystyrene equivalent weight average molecular weight (Mw) was measured using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Comparative Synthesis Example 1
A reaction was performed in the same manner as in Synthesis Example 1 except that azobisbutyronitrile was used instead of V-601 as a radical polymerization initiator, to obtain a resin A2. This resin A2 had a polystyrene equivalent weight average molecular weight of 8,000.

Example 1
100 parts by mass of the resin A1, 22 parts by mass of the compound represented by the formula (4), (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate [Rhodorsil Photoinitiator 2074 (manufactured by Rhodia)] 2 parts by mass, 88 parts by mass of γ-butyrolactone, and 352 parts by mass of ethyl lactate were mixed at 23 ° C., and then filtered through a polytetrafluoroethylene cartridge filter having a pore size of 0.2 μm to obtain a radiation-sensitive resin composition. Got.

(In formula (4), Q ⁴ represents a substituent represented by formula (4-1).)

The radiation-sensitive resin composition obtained above is spin-coated on a 4-inch silicon wafer (2), and heated (prebaked) at 100 ° C. for 2 minutes using a hot plate, the radiation-sensitive resin composition layer (1 The film thickness was measured using a film thickness meter [Lambda Ace (Dainippon Screen Mfg. Co., Ltd.)] and found to be 2.6 μm [see FIG. 1 (a)].
Thereafter, radiation was passed through the mask (3) using an i-line stepper [NSR-1755i7A (NA = 0.5); manufactured by Nikon Corporation] on the obtained radiation-sensitive resin composition layer (1). (4) was irradiated and exposed [see FIG. 1 (b)]. As the mask (3), a mask for forming a contact hole pattern having a line width of 3 μm in a cured resin pattern with an interval of 9 μm was used.

After the exposure, the film was developed by dipping in a 0.4% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. for 70 seconds, washed with ultrapure water, and dried. In the pattern after development, the effective sensitivity was 120 mJ / cm ^{2 when} the exposure amount in the mask exposure in which the diameter of the contact hole was 3 μm was defined as the effective sensitivity. After drying, the whole surface was irradiated with radiation using a DUV lamp [UXM-501MD; manufactured by USHIO INC.] (Intensity of 300 mJ / cm ^{2 based on the} wavelength of 313 nm), and in a clean oven at 220 ° C. Heated for 30 minutes to form a cured resin pattern (5) [see FIG. 1 (c)].
It was 2.1 micrometers when the thickness (T1) of the obtained cured resin pattern (5) was measured using the film thickness meter [DEKTAK3; made by ULVAC, Inc.].

  Visible light transmittance was determined by forming a cured resin film on the transparent glass substrate [# 1737; manufactured by Corning Co., Ltd.] by the above-described method except that the stepper exposure process was not performed, and the microspectrophotometer [OSP-200; Olympus Optics). Manufactured by Kogyo Co., Ltd.]. The film thickness was measured with a film thickness meter [DEKTAK3; manufactured by ULVAC, Inc.]. The average light transmittance at a wavelength of 400 nm per 1 μm of the obtained cured resin film was as high as 96.2%, and no coloring was observed. Moreover, as a result of performing the solvent resistance test by immersing the board | substrate with which the cured resin pattern was formed in methyl ethyl ketone or N-methylpyrrolidone (23 degreeC) for 30 minutes, all were not seen before and after immersion.

Comparative Example 1
A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that the resin A2 was used.
As a result of performing the same operation as in Example 1, the thickness (T1) of the cured resin pattern (5) obtained with an effective sensitivity of 145 mJ / cm ² was 2.0 μm. The average light transmittance at a wavelength of 400 nm per 1 μm of the film was 94.4%.

  The radiation sensitive resin composition of the present invention is a TFT insulating film used in TFT type liquid crystal display devices and organic EL display devices, a diffuse reflector used in a reflective TFT substrate, an organic EL insulating film, and a CCD protection. It is useful as a material for forming a cured resin pattern including a film.

It is a schematic diagram which shows the process of forming a cured film using the radiation sensitive resin composition of this invention.

Explanation of symbols

1 .. Radiation sensitive resin composition layer 11. Unirradiated region 12. Irradiated region 2. Substrate 3. Mask 4. Radiation 5. Resin pattern 6. Cured resin pattern

Claims (8)

  In the radiation-sensitive resin composition containing the curable alkali-soluble resin (A), the quinonediazide compound (B), and the solvent (C), the curable alkali-soluble resin (A) does not have a nitrile group. A radiation-sensitive resin composition, which is a polymer obtained by polymerization using an azo radical polymerization initiator (ai). The radiation sensitive resin composition according to claim 1, wherein the radical polymerization initiator (ai) having no nitrile group is represented by the formula (1).

In Expression ^(1), R 1 ~R ⁴ each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms.
A ¹ and A ² are each independently an optionally substituted alkyl group having 1 to 6 carbon atoms, a substituent represented by formula (2), or a substituent represented by formula (3). Represents.

In formula (2) and formula (3), X ¹ and X ² each independently represent a group or atom selected from the group consisting of NR ⁷ , O and S.
Y ¹ and Y ² each independently represent a single bond or a group or atom selected from the group consisting of N (R ⁸ ), O and S.
R ⁵ , R ⁶ and R ⁸ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
R ⁷ represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ]   The curable alkali-soluble resin (A) is a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group. The radiation-sensitive resin composition according to claim 1 or 2, wherein the unsaturated compound leading to the structural unit (a2) is not an unsaturated carboxylic acid.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the curable group in the structural unit (a2) is an oxetanyl group.   The constitution in which the curable alkali-soluble resin (A) is further derived from a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond and an aromatic compound having a polymerizable carbon-carbon unsaturated bond. Claims comprising at least one structural unit (a3) selected from the group consisting of a unit (a32), a structural unit (a33) derived from a vinyl cyanide compound, and a structural unit (a34) derived from an N-substituted maleimide compound Item 5. The composition according to any one of Items 1 to 4.   The cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-5.   A radiation-sensitive resin composition according to any one of claims 1 to 5 is applied onto a substrate, the solvent is removed, radiation is applied through a mask, and then development is performed with an alkaline aqueous solution to form a predetermined pattern. Then, the manufacturing method of the cured resin pattern characterized by irradiating radiation to the whole pattern surface on a board | substrate. The manufacturing method of the cured resin pattern of Claim 7 which heats, after irradiating a radiation to the pattern whole surface on a board | substrate.

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