CN1903942A - Radiation sensitive resin composition - Google Patents

Radiation sensitive resin composition Download PDF

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Publication number
CN1903942A
CN1903942A CNA2005100849279A CN200510084927A CN1903942A CN 1903942 A CN1903942 A CN 1903942A CN A2005100849279 A CNA2005100849279 A CN A2005100849279A CN 200510084927 A CN200510084927 A CN 200510084927A CN 1903942 A CN1903942 A CN 1903942A
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sulfonium
compound
methyl
acid
composition
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川口裕次郎
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种辐射敏感的树脂组合物，该组合物包含(A)具有硬化性的碱溶性树脂，(B)醌二叠氮化合物和(C)溶剂，其中溶剂(C)含有通式(1)的化合物和乳酸烷基酯。R1－O－[CH(CH3)CH2O]n－R2 (1)。通式(1)中，R1和R2独立地表示含有1～4个碳原子的烷基，n表示1～4的整数。A radiation-sensitive resin composition comprising (A) a hardening alkali-soluble resin, (B) a quinonediazide compound and (C) a solvent, wherein the solvent (C) contains a compound of the general formula (1) compounds and alkyl lactates. R 1 -O-[CH(CH 3 )CH 2 O] n -R 2 (1). In the general formula (1), R 1 and R 2 independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.

Description

Radiosensitive resin combination
Technical field
The present invention relates to a kind of radiosensitive resin combination.
Background technology
Radiosensitive resin combination can be used as the material that forms the hardening resin pattern; typically comprise thin film transistor (below; be called TFT in some cases) insulating film of used TFT in the type liquid-crystal display; the diffusion reflector that uses in the reflection-type TFT substrate; organic EL insulating film, protective membrane of charge (below, be called CCD in some cases) etc. (referring to; Japanese Patent 2933879, Japanese Patent Application Publication (JP-A) 9-244009).
Recently, according to a kind of large-size glass substrate that is used to make the TFT substrate, the application method of composition is changed into not the seam of rotary substrate from spin-coating method be coated with method (slit coating) (referring to, JP-A No.2001-162204, JP-A No.2003-211053, JP-A No.8-173875).Be coated with in order to stitch, the radiosensitive resin combination that requires to be used for stainless steel-based bottom material has excellent wettability (wettability).
But, when the conventional radiation-sensitive resin composition that will use ethyl lactate as solvent is used for seam when being coated with method, its wettability poor (referring to, JP-A No.2002-240422).
Description of drawings
Fig. 1
Embodiment: when the radiosensitive resin combination that uses embodiment is judged flowability, the track of radiosensitive resin combination.
Comparative example: when the radiation-sensitive resin composition that uses comparative example is judged flowability, the track of radiation-sensitive resin composition.
Summary of the invention
An object of the present invention is to provide a kind of radiosensitive resin combination that excellent wetting property is arranged for the substrate of making by stainless steel.
The inventor studies to find a kind of radiosensitive resin combination that has the problems referred to above hardly, found that the radiation-sensitive resin composition that comprises the solvent that contains a kind of ether compound, when using it for seam when being coated with method, have excellent wetting property, thereby finished the present invention.
That is, the invention provides following [1]～[11].
[1], a kind of radiation-sensitive resin composition, said composition comprises (A) and has indurative alkali soluble resins, (B) quinone di-azido compound and (C) solvent, wherein solvent (C) contains the compound and the lactic acid alkyl ester of general formula (1).
R 1-O-[CH(CH 3)CH 2O] n-R 2 (1)
[in the general formula (1), R 1And R 2Expression contains the alkyl of 1～4 carbon atom independently, and n represents 1～4 integer.]
[2], the composition of [1], wherein R 1And R 2Represent methyl or ethyl independently.
[3], the composition of [1] or [2], wherein n represents integer 2 or 3.
[4], any one composition of [1]～[3], wherein the content of solvent (C) is 75%～88 weight % based on the total amount of radiosensitive resin combination.
[5], any one composition of [1]～[4], the content of its formula of (1) compound is 50～99 weight % based on the solvent total amount.
[6], any one composition of [1]～[5], wherein the content of lactic acid alkyl ester is 1～50 weight % based on the solvent total amount.
[7], any one composition of [1]～[6], the alkali soluble resins (A) that wherein has sclerosis character is a kind of multipolymer, this multipolymer comprise derived from unsaturated carboxylic acid component units (a1) and derived from the component units (a2) of the unsaturated compound (except the unsaturated carboxylic acid) that contains sclerosis base.
[8], the composition of [7], wherein in the component units (a2) derived from the unsaturated compound (except the unsaturated carboxylic acid) that contains the sclerosis base, the sclerosis base is an oxetanyl.
[9], any one composition of [1]～[8], the alkali soluble resins (A) that wherein has sclerosis character is a kind of multipolymer that also comprises at least a component units (a3), and described component units (a3) is selected from: the component units (a34) that obtains derived from the component units (a31) of the carboxylicesters that contains olefinic double bond, derived from the component units (a33) of the component units (a32) of the aromatic ethenyl compound that contains the polymerizable carbon-to-carbon unsaturated bond, derived from ethylene base cyanogen compound and the unsaturated link(age) fracture by N-substituted maleimide amine compound.
[10], a kind of hardening resin pattern that forms by any one composition of [1]～[9].
[11], the indicating meter of the hardening resin pattern of a kind of comprising [10].
Detailed Description Of The Invention
Will describe the present invention in detail below.
The alkali soluble resins (A) that uses among preferred the present invention with sclerosis character be a kind of comprise derived from unsaturated carboxylic acid component units (a1) and derived from the multipolymer of the component units (a2) of the unsaturated compound (except the unsaturated carboxylic acid) that contains the sclerosis base.
As for above-mentioned unsaturated carboxylic acid, can mention the unsaturated carboxylic acid that contains one or more carboxyl in the molecule, for example, undersaturated monocarboxylic acid, undersaturated di-carboxylic acid etc., its specific examples comprises vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid etc.
The above-mentioned unsaturated compound (except the unsaturated carboxylic acid) that contains the sclerosis base comprises the unsaturated compound that contains epoxy group(ing), (methyl) glycidyl acrylate for example, (methyl) vinylformic acid Beta-methyl glycidyl ester, (methyl) propenoic acid beta-ethyl glycidyl ester, 3-methyl-3,4-epoxy butyl (methyl) acrylate, 3-ethyl-3,4-epoxy butyl (methyl) acrylate, 4-methyl-4,5-epoxy amyl group (methyl) acrylate, 2,3-epoxycyclohexyl methyl (methyl) acrylate, 3,4-epoxycyclohexyl methyl (methyl) acrylate, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, 2-vinyl cyclohexene oxygen, 3-vinyl cyclohexene oxygen, 4 vinyl cyclohexene oxygen etc.; The unsaturated compound that contains oxetanyl, 3-(methyl) acryloyl-oxy methyl trimethylene oxide for example, 3-methyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 3-ethyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-phenyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-trifluoromethyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-pentafluoroethyl group-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 3-methyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-phenyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-trifluoromethyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-pentafluoroethyl group-3-(methyl) acrylyl oxy-ethyl trimethylene oxide etc.
The preferred unsaturated compound that contains oxetanyl that uses, 3-(methyl) acryloyl-oxy methyl trimethylene oxide for example, 3-methyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 3-ethyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-phenyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-trifluoromethyl-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 2-pentafluoroethyl group-3-(methyl) acryloyl-oxy methyl trimethylene oxide, 3-methyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 3-methyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-phenyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-trifluoromethyl-3-(methyl) acrylyl oxy-ethyl trimethylene oxide, 2-pentafluoroethyl group-3-(methyl) acrylyl oxy-ethyl trimethylene oxide etc. more preferably use 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide.
When the alkali soluble resins that comprises the unsaturated compound that contains oxetanyl when use prepares radiation-sensitive resin composition, the trend of excellent storage stability occurs having, this is preferred.
Multipolymer of the present invention can also comprise at least a component units (a3), and this component units (a3) is selected from: the component units (a34) that obtains derived from the component units (a31) of the carboxylicesters that contains olefinic double bond, derived from the component units (a33) of the component units (a32) of the aromatic ethenyl compound that contains the polymerizable carbon-to-carbon unsaturated bond, derived from ethylene base cyanogen compound and the unsaturated link(age) fracture by N-substituted maleimide amine compound.
The above-mentioned example that contains the carboxylicesters deutero-(a31) of olefinic double bond comprises esters of unsaturated carboxylic acids, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid two ring pentyl esters, (methyl) phenyl acrylate, ethyl maleate, DEF, diethyl itaconate etc.; Unsaturated aminoalkyl group carboxylicesters, for example (methyl) acrylic-amino ethyl ester etc.Vinyl carboxylates, vinyl-acetic ester for example, propionate etc.
The above-mentioned example that contains the aromatics deutero-(a32) of polymerizable carbon-to-carbon unsaturated bond comprises aromatic ethenyl compound etc.The example of aromatic ethenyl compound comprises vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.
The example of above-mentioned vinyl cyanide compound deutero-(a33) comprises vinyl cyanide compound, vinyl cyanide for example, methacrylonitrile, alpha-chloro (methyl) vinyl cyanide etc.
The example of above-mentioned N-substituted maleimide amine compound deutero-(a34) comprises N-methyl maleimide; the N-ethyl maleimide; the N-butyl maleimide; N-cyclohexyl maleimide; N-benzyl maleimide; N-phenylmaleimide; N-(4-acetylphenyl) maleimide; N-(2,6-diethyl phenyl) maleimide, N-(4-dimethylamino-3; the 5-dinitrophenyl) maleimide; N-succinimido-3-maleimide benzoate, N-succinimido-3-maleimide propionic salt, N-succinimido-4-maleimide butyrates; N-succinimido-6-maleimide hexanoate; N-(1-anilino naphthyl-4)-maleimide, N-[4-(2-benzoxazolyl) phenyl]-maleimide, N-(9-acridyl) maleimide etc.
Such component units can use separately also and can two or morely be used in combination.
In the component units (a1) and multipolymer that comprise derived from unsaturated carboxylic acid derived from the component units (a2) that contains the basic unsaturated compound (except the unsaturated carboxylic acid) of sclerosis, (a1) ratio of components based on multipolymer component units total mole number is generally 5～50 moles of %, be preferably 15～40 moles of %, and (a2) be generally 95～50 moles of % based on the ratio of components of multipolymer component units total mole number, be preferably 85～60 moles of %.
When (a1) in the above-mentioned multipolymer and ratio of components (a2) are within above-mentioned scope, following preferred trend is arranged: when forming pattern, demonstrate the dissolution rate and the resulting pattern that are suitable for photographic developer and also demonstrate high hardening.
Comprise (a1) and multipolymer (a2) among the present invention and can comprise other component units as except that (a1) with the optional components (a2).When multipolymer comprises other component units as optional components, ratio based on (a1) of multipolymer component units total mole number is generally 5～50 moles of %, be preferably 15～40 moles of %, and the ratio based on (a2) of identical standard is generally 95～5 moles of %, is preferably 85～15 moles of %.In addition, when multipolymer comprised other component units, its ratio was preferably 0.1～90 mole of % based on identical standard, more preferably 5～80 moles of %.
The example that comprises (a1) and multipolymer (a2) among the present invention comprises 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/benzyl methacrylate/Sipacril 2739OF, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/benzyl methacrylate/methacrylic acid/styrol copolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/styrol copolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/cyclohexyl methacrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/methylmethacrylate copolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/methyl methacrylate/styrol copolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/methacrylic tert-butyl acrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/isobornyl methacrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/benzyl acrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/cyclohexyl acrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/isobornyl acrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/methacrylic acid two ring pentyl ester multipolymers, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/tert-butyl acrylate multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/phenyl maleimide multipolymer, 3-ethyl-3-methacryloxypropyl methyl trimethylene oxide/methacrylic acid/cyclohexyl maleimide copolymer etc.
According to the GPC method, the weight-average molecular weight that, comprises (a1) and multipolymer (a2) among the present invention based on polystyrene calibration standards is generally 2,000～100, and 000, be preferably 2,000～50,000, more preferably 3,000～20,000.In the time of within the weight-average molecular weight based on polystyrene calibration standards is in above-mentioned scope, trend towards obtaining high developing powder, keeping the residual film ratio simultaneously in development, this is preferred.
The content that comprises (a1) and multipolymer (a2) in the radiation-sensitive resin composition of the present invention based on the solids content of radiosensitive resin combination, is generally 50～90 weight %, is preferably 60～90 weight %.
The example of quinone di-azido compound among the present invention (B) comprises 1,2-benzoquinones two nitrine sulfonate, 1,2-naphthoquinones two nitrine sulfonate, 1,2-benzoquinones two nitrine sulphonamide, 1,2-naphthoquinones two nitrine sulphonamide etc.
Its specific examples comprises 1 of trihydroxybenzophenone, 2-naphthoquinones two nitrine sulfonate, for example
2,3,4-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,3,4-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
2,4,6-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,4,6-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate etc.;
1 of tetrahydroxybenzophenone, 2-naphthoquinones two nitrine sulfonate, for example
2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
2,3,4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,3,4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-naphthoquinones two nitrine-5-sulfonate etc.;
1 of pentahydroxybenzophenone, 2-naphthoquinones two nitrine sulfonate, for example
2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulfonate etc.;
1 of hexahydroxy-benzophenone, 2-naphthoquinones two nitrine sulfonate, for example
2,4,6,3 ', 4 ', 5 '-hexahydroxy-benzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
2,4,6,3 ', 4 ', 5 '-hexahydroxy-benzophenone-1,2-naphthoquinones two nitrine-5-sulfonate,
3,4,5,3 ', 4 ', 5 '-hexahydroxy-benzophenone-1,2-naphthoquinones two nitrine-4-sulfonate,
3,4,5,3 ', 4 ', 5 '-hexahydroxy-benzophenone-1,2-naphthoquinones two nitrine-5-sulfonate etc.;
1 of (poly-hydroxy phenyl) alkane, 2-naphthoquinones two nitrine sulfonate, for example
Two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-4-sulfonate,
Two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-5-sulfonate,
Two (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-4-sulfonate,
Two (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-5-sulfonate,
1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones two nitrine-4-sulfonate,
1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones two nitrine-5-sulfonate,
Two (2,3,4-trihydroxy-phenyl) methane-1,2-naphthoquinones two nitrine-4-sulfonate,
Two (2,3,4-trihydroxy-phenyl) methane-1,2-naphthoquinones two nitrine-5-sulfonate,
2,2 '-two (2,3,4-trihydroxy-phenyl) propane-1,2-naphthoquinones two nitrine-4-sulfonate,
2,2 '-two (2,3,4-trihydroxy-phenyl) propane-1,2-naphthoquinones two nitrine-5-sulfonate,
1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones two nitrine-4-sulfonate,
1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones two nitrine-5-sulfonate,
4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones two nitrine-4-sulfonate,
4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones two nitrine-5-sulfonate,
Two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-4-sulfonate,
Two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-5-sulfonate,
3,3,3 ', 3 '-tetramethyl--1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones two nitrine-4-sulfonate,
3,3,3 ', 3 '-tetramethyl--1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones two nitrine-5-sulfonate,
2,2,4-trimethylammonium-7,2 ', 4 '-trihydroxy-flavane-1,2-naphthoquinones two nitrine-4-sulfonate,
2,2,4-trimethylammonium-7,2 ', 4 '-trihydroxy-flavane-1,2-naphthoquinones two nitrine-5-sulfonate etc.
Above-mentioned quinone di-azido compound (B) uses separately or two or more being used in combination.The content of quinone di-azido compound among the present invention (B) based on the solids content of radiosensitive resin combination, is generally 2～50 weight %, is preferably 5～40 weight %.When the content of quinone di-azido compound is within above-mentioned scope, by strengthening the difference of dissolution rate between unexposed portion and the exposed portion, the trend of the development film residual ratio that keeps high is arranged, be preferred.
The solids content of radiosensitive resin combination of herein mentioning is meant that radiation-sensitive resin composition desolventizes (C) outer total mass.
The solvent (C) that uses in the radiosensitive resin combination of the present invention comprises general formula (1) compound and ethyl lactate.Alkyl represents to contain the alkyl of 1～4 carbon atom.
R 1-O-[CH(CH 3)CH 2O] n-R 2 (1)
[in the general formula (1), R 1And R 2Expression contains the alkyl of 1～4 carbon atom independently, and n represents 1～4 integer.]
The specific examples that contains the alkyl of 1～4 carbon atom comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl and the tertiary butyl.In the middle of them, preferably should be mentioned that methyl, ethyl, n-propyl and sec.-propyl more preferably should be mentioned that methyl and ethyl.
The specific examples of general formula (1) compound comprises the propylene glycol dimethyl ether, propylene glycol ethyl-methyl ether, the propylene glycol Anaesthetie Ether, the dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol Anaesthetie Ether, the tripropylene glycol dimethyl ether, tripropylene glycol ethyl-methyl ether, tripropylene glycol Anaesthetie Ether, four propylene glycol dimethyl ethers, four propylene glycol ethyl-methyl ethers, four propylene glycol Anaesthetie Ethers etc. preferably should be mentioned that the dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, the dipropylene glycol Anaesthetie Ether, the tripropylene glycol dimethyl ether, tripropylene glycol ethyl-methyl ether, tripropylene glycol Anaesthetie Ether, more preferably should be mentioned that the dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol Anaesthetie Ether, tripropylene glycol dimethyl ether, the tripropylene glycol Anaesthetie Ether, also more preferably should be mentioned that the dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol Anaesthetie Ether.
General formula (1) compound is independent or two or more being used in combination.
The specific examples of lactic acid alkyl ester comprises methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate, isobutyl lactate, the secondary butyl ester of lactic acid, the lactic acid tert-butyl esters etc. preferably should be mentioned that ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate more preferably should be mentioned that ethyl lactate, lactic acid n-propyl ester, n-butyl lactate.
Lactic acid alkyl ester is independent or two or more being used in combination.
Above-mentioned general formula (1) compound and lactic acid alkyl ester can use with other solvent.
Above-mentioned example that can the blended solvent comprises ethylene glycol one alkyl oxide, ethylene glycol monomethyl ether for example, ethylene glycol monoethyl ether, ethylene glycol one propyl ether, ethylene glycol monobutyl ether etc.;
The glycol ether dialkyl ether, diethylene glycol dimethyl ether for example, diethylene glycol diethyl ether, glycol ether dipropyl ether, glycol ether dibutyl ether etc.;
Ethylene glycol alkyl oxide acetic ester, methylcellosolve acetate for example, ethyl cellosolve acetate etc.;
Propylene glycol alkyl ether acetic acid ester, Glycol Monomethyl ether acetic ester for example, propylene glycol monoethyl ether acetic ester, propylene glycol one propyl ether acetic ester etc.;
Arene, benzene for example, toluene, dimethylbenzene etc.;
Ketone, methyl ethyl ketone for example, acetone, Methyl amyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.;
Alcohols, ethanol for example, propyl alcohol, butanols, hexanol, hexalin, 1,2 ethylene glycol, glycerine etc.;
The cyclic ester class, ethylene carbonate for example, Texacar PC, butyrolactone etc.;
The ester class, 3-ethoxyl ethyl propionate for example, 3-methoxypropionic acid methyl esters, 2-hydroxy-methyl isobutyl acid, butylacetate, pentyl acetate, Pyruvic Acid Methyl ester etc.
The content of solvent (C) based on radiosensitive resin combination, is generally 75～88 weight %, is preferably 80～88 weight %, more preferably 82～88 weight %.When solvent (C) content is within above-mentioned scope, obtain low viscous composition easily, this is preferred.
The content of general formula (1) compound based on the total amount of solvent (C), is preferably 50～99 weight %, 55～99 weight % more preferably, also more preferably 60～99 weight %.When the content of general formula (1) compound is within above-mentioned scope, can obtain low viscous composition and improve the wetting property of substrate, this is preferred.
The content of lactic acid alkyl ester based on the total amount of solvent (C), is preferably 1～50 weight %, 1～45 weight % more preferably, also more preferably 1～40 weight %.When the content of lactic acid alkyl ester was within above-mentioned scope, the wetting property of substrate was tending towards improving, and the solubleness of composition component is tending towards uprising, and this is preferred.
Radiosensitive resin combination of the present invention can comprise, polymerization starter (D), and polyphenolic compound (E), linking agent (F), polymerisable monomer (G), and silane coupling agent (H) are as other components.
As for polymerization starter (D), mention salt as cationic polymerization initiators.Salt is to constitute by positively charged ion with derived from lewis acidic negatively charged ion.
Above-mentioned cationic specific examples comprises phenylbenzene iodine, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to the octadecyl phenyl) iodine, two (to octyloxyphenyl) iodine, two (to octadecane oxygen base phenyl) iodine, phenyl (to octadecane oxygen base phenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, triphenylsulfonium, three (p-methylphenyl) sulfonium, three (p-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (to tert-butyl-phenyl) sulfonium, three (to cyano-phenyl) sulfonium, three (rubigan) sulfonium, dimethyl (methoxyl group) sulfonium, dimethyl (oxyethyl group) sulfonium, dimethyl (propoxy-) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert.-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluorine methoxyl group) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromine propoxy-) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium, dimethyl (three (trichloromethyl) methyl) sulfoniums etc. preferably should be mentioned that two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium, three (to tert-butyl-phenyl) sulfonium etc.
Above-mentionedly comprise hexafluoro-phosphate radical derived from lewis acidic anionic specific examples, the hexafluoroarsenate root, hexafluoroantimonic anion, four (pentafluorophenyl group) borates etc. preferably should be mentioned that hexafluoroantimonic anion and four (pentafluorophenyl group) borate.
Above-mentioned positively charged ion and can optional combination derived from lewis acidic negatively charged ion.
The specific examples of cationic polymerization initiators comprises phosphofluoric acid phenylbenzene iodine, two (p-methylphenyl) iodine of phosphofluoric acid, two (to the tert-butyl-phenyl) iodine of phosphofluoric acid, two (to the octyl phenyl) iodine of phosphofluoric acid, two (to the octadecyl phenyl) iodine of phosphofluoric acid, two (to the octyloxyphenyl) iodine of phosphofluoric acid, two (to the octadecane oxygen base phenyl) iodine of phosphofluoric acid, phosphofluoric acid phenyl (to octadecane oxygen base phenyl) iodine, phosphofluoric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, phosphofluoric acid methyl naphthalene iodide, phosphofluoric acid ethyl naphthalene iodide, the phosphofluoric acid triphenylsulfonium, phosphofluoric acid three (p-methylphenyl) sulfonium, phosphofluoric acid three (p-isopropyl phenyl) sulfonium, phosphofluoric acid three (2, the 6-3,5-dimethylphenyl) sulfonium, phosphofluoric acid three (to tert-butyl-phenyl) sulfonium, phosphofluoric acid three (to cyano-phenyl) sulfonium, phosphofluoric acid three (rubigan) sulfonium, phosphofluoric acid dimethyl naphthyl sulfonium, phosphofluoric acid diethyl naphthyl sulfonium, phosphofluoric acid dimethyl (methoxyl group) sulfonium, phosphofluoric acid dimethyl (oxyethyl group) sulfonium, phosphofluoric acid dimethyl (propoxy-) sulfonium, phosphofluoric acid dimethyl (butoxy) sulfonium, phosphofluoric acid dimethyl (octyloxy) sulfonium, phosphofluoric acid dimethyl (octadecane oxygen base) sulfonium, phosphofluoric acid dimethyl (isopropoxy) sulfonium, phosphofluoric acid dimethyl (tert.-butoxy) sulfonium, phosphofluoric acid dimethyl (cyclopentyloxy) sulfonium, phosphofluoric acid dimethyl (cyclohexyloxy) sulfonium, phosphofluoric acid dimethyl (fluorine methoxyl group) sulfonium, phosphofluoric acid dimethyl (2-chloroethoxy) sulfonium, phosphofluoric acid dimethyl (3-bromine propoxy-) sulfonium, phosphofluoric acid dimethyl (4-cyano group butoxy) sulfonium, phosphofluoric acid dimethyl (8-nitro octyloxy) sulfonium, phosphofluoric acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, phosphofluoric acid dimethyl (2-hydroxyl isopropoxy) sulfonium, phosphofluoric acid dimethyl (three (trichloromethyl) methyl) sulfonium
Hexafluoroarsenate phenylbenzene iodine, two (p-methylphenyl) iodine of hexafluoroarsenate, two (to the tert-butyl-phenyl) iodine of hexafluoroarsenate, two (to the octyl phenyl) iodine of hexafluoroarsenate, two (to the octadecyl phenyl) iodine of hexafluoroarsenate, two (to the octyloxyphenyl) iodine of hexafluoroarsenate, two (to the octadecane oxygen base phenyl) iodine of hexafluoroarsenate, hexafluoroarsenate phenyl (to octadecane oxygen base phenyl) iodine, hexafluoroarsenate (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoroarsenate methyl naphthalene iodide, hexafluoroarsenate ethyl naphthalene iodide, the hexafluoroarsenate triphenylsulfonium, hexafluoroarsenate three (p-methylphenyl) sulfonium, hexafluoroarsenate three (p-isopropyl phenyl) sulfonium, hexafluoroarsenate three (2, the 6-3,5-dimethylphenyl) sulfonium, hexafluoroarsenate three (to tert-butyl-phenyl) sulfonium, hexafluoroarsenate three (to cyano-phenyl) sulfonium, hexafluoroarsenate three (rubigan) sulfonium, hexafluoroarsenate dimethyl naphthyl sulfonium, hexafluoroarsenate diethyl naphthyl sulfonium, hexafluoroarsenate dimethyl (methoxyl group) sulfonium, hexafluoroarsenate dimethyl (oxyethyl group) sulfonium, hexafluoroarsenate dimethyl (propoxy-) sulfonium, hexafluoroarsenate dimethyl (butoxy) sulfonium, hexafluoroarsenate dimethyl (octyloxy) sulfonium, hexafluoroarsenate dimethyl (octadecane oxygen base) sulfonium, hexafluoroarsenate dimethyl (isopropoxy) sulfonium, hexafluoroarsenate dimethyl (tert.-butoxy) sulfonium, hexafluoroarsenate dimethyl (cyclopentyloxy) sulfonium, hexafluoroarsenate dimethyl (cyclohexyloxy) sulfonium, hexafluoroarsenate dimethyl (fluorine methoxyl group) sulfonium, hexafluoroarsenate dimethyl (2-chloroethoxy) sulfonium, hexafluoroarsenate dimethyl (3-bromine propoxy-) sulfonium, hexafluoroarsenate dimethyl (4-cyano group butoxy) sulfonium, hexafluoroarsenate dimethyl (8-nitro octyloxy) sulfonium, hexafluoroarsenate dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, hexafluoroarsenate dimethyl (2-hydroxyl isopropoxy) sulfonium, hexafluoroarsenate dimethyl (three (trichloromethyl) methyl) sulfonium
Hexafluoro-antimonic acid phenylbenzene iodine, two (p-methylphenyl) iodine of hexafluoro-antimonic acid, two (to the tert-butyl-phenyl) iodine of hexafluoro-antimonic acid, two (to the octyl phenyl) iodine of hexafluoro-antimonic acid, two (to the octadecyl phenyl) iodine of hexafluoro-antimonic acid, two (to the octyloxyphenyl) iodine of hexafluoro-antimonic acid, two (to the octadecane oxygen base phenyl) iodine of hexafluoro-antimonic acid, hexafluoro-antimonic acid phenyl (to octadecane oxygen base phenyl) iodine, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, hexafluoro-antimonic acid methyl naphthalene iodide, hexafluoro-antimonic acid ethyl naphthalene iodide, the hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (p-methylphenyl) sulfonium, hexafluoro-antimonic acid three (p-isopropyl phenyl) sulfonium, hexafluoro-antimonic acid three (2, the 6-3,5-dimethylphenyl) sulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, hexafluoro-antimonic acid three (to cyano-phenyl) sulfonium, hexafluoro-antimonic acid three (rubigan) sulfonium, hexafluoro-antimonic acid dimethyl naphthyl sulfonium, hexafluoro-antimonic acid diethyl naphthyl sulfonium, hexafluoro-antimonic acid dimethyl (methoxyl group) sulfonium, hexafluoro-antimonic acid dimethyl (oxyethyl group) sulfonium, hexafluoro-antimonic acid dimethyl (propoxy-) sulfonium, hexafluoro-antimonic acid dimethyl (butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (octyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (octadecane oxygen base) sulfonium, hexafluoro-antimonic acid dimethyl (isopropoxy) sulfonium, hexafluoro-antimonic acid dimethyl (tert.-butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (cyclopentyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (cyclohexyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (fluorine methoxyl group) sulfonium, hexafluoro-antimonic acid dimethyl (2-chloroethoxy) sulfonium, hexafluoro-antimonic acid dimethyl (3-bromine propoxy-) sulfonium, hexafluoro-antimonic acid dimethyl (4-cyano group butoxy) sulfonium, hexafluoro-antimonic acid dimethyl (8-nitro octyloxy) sulfonium, hexafluoro-antimonic acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, hexafluoro-antimonic acid dimethyl (2-hydroxyl isopropoxy) sulfonium, hexafluoro-antimonic acid dimethyl (three (trichloromethyl) methyl) sulfonium
Four (pentafluorophenyl group) boric acid phenylbenzene iodine, two (p-methylphenyl) iodine of four (pentafluorophenyl group) boric acid, two (to the tert-butyl-phenyl) iodine of four (pentafluorophenyl group) boric acid, two (to the octyl phenyl) iodine of four (pentafluorophenyl group) boric acid, two (to the octadecyl phenyl) iodine of four (pentafluorophenyl group) boric acid, two (to the octyloxyphenyl) iodine of four (pentafluorophenyl group) boric acid, two (to the octadecane oxygen base phenyl) iodine of four (pentafluorophenyl group) boric acid, four (pentafluorophenyl group) boric acid phenyl (to octadecane oxygen base phenyl) iodine, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, four (pentafluorophenyl group) boric acid methyl naphthalene iodide, four (pentafluorophenyl group) boric acid ethyl naphthalene iodide, four (pentafluorophenyl group) boric acid triphenylsulfonium, four (pentafluorophenyl group) boric acid three (p-methylphenyl) sulfonium, four (pentafluorophenyl group) boric acid three (p-isopropyl phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (2, the 6-3,5-dimethylphenyl) sulfonium, four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (to cyano-phenyl) sulfonium, four (pentafluorophenyl group) boric acid three (rubigan) sulfonium, four (pentafluorophenyl group) boric acid dimethyl naphthyl sulfonium, four (pentafluorophenyl group) boric acid diethyl naphthyl sulfonium, four (pentafluorophenyl group) boric acid dimethyl (methoxyl group) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (oxyethyl group) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (propoxy-) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (octyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (octadecane oxygen base) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (isopropoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (tert.-butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (cyclopentyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (cyclohexyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (fluorine methoxyl group) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (2-chloroethoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (3-bromine propoxy-) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (4-cyano group butoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (8-nitro octyloxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (2-hydroxyl isopropoxy) sulfonium, four (pentafluorophenyl group) boric acid dimethyl (three (trichloromethyl) methyl) sulfonium etc.
Preferably should be mentioned that two (p-methylphenyl) iodine of phosphofluoric acid, phosphofluoric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of phosphofluoric acid, the phosphofluoric acid triphenylsulfonium, phosphofluoric acid three (to tert-butyl-phenyl) sulfonium, two (p-methylphenyl) iodine of hexafluoroarsenate, hexafluoroarsenate (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of hexafluoroarsenate, the hexafluoroarsenate triphenylsulfonium, hexafluoroarsenate three (to tert-butyl-phenyl) sulfonium, two (p-methylphenyl) iodine of hexafluoro-antimonic acid, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of hexafluoro-antimonic acid, hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, two (p-methylphenyl) iodine of four (pentafluorophenyl group) boric acid, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of four (pentafluorophenyl group) boric acid, four (pentafluorophenyl group) boric acid triphenylsulfonium, four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium etc.
More preferably should be mentioned that two (p-methylphenyl) iodine of hexafluoro-antimonic acid, hexafluoro-antimonic acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of hexafluoro-antimonic acid, the hexafluoro-antimonic acid triphenylsulfonium, hexafluoro-antimonic acid three (to tert-butyl-phenyl) sulfonium, two (p-methylphenyl) iodine of four (pentafluorophenyl group) boric acid, four (pentafluorophenyl group) boric acid (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to the tert-butyl-phenyl) iodine of four (pentafluorophenyl group) boric acid, four (pentafluorophenyl group) boric acid triphenylsulfonium, four (pentafluorophenyl group) boric acid three (to tert-butyl-phenyl) sulfonium etc.
When using polymerization starter (D), its content is generally 0.01～10 weight % based on the solids content of radiosensitive resin combination, is preferably 0.1～5 weight %.When the content of polymerization starter (D) was within above-mentioned scope, by improving the setting rate of heat embrittlement, the reduction of heat embrittlement intermediate-resolution was tending towards being suppressed, and the solvent resistance of cured film is tending towards improving, and this is preferred.
As for polyphenolic compound (E), should be mentioned that and contain two or more polyhydric compound in the molecule.The example of above-mentioned polyphenolic compound comprises polyphenol, trihydroxybenzophenone for example, and tetrahydroxybenzophenone, pentahydroxybenzophenone, the hexahydroxy-benzophenone, (poly-hydroxy phenyl) alkane etc., these are compounds of mentioning equally in quinone di-azido compound.
As for above-mentioned polyphenolic compound (E), should be mentioned that the polymkeric substance that obtains as a kind of starting material monomer with hydroxy styrenes at least.As for polyphenolic compound (E), specifically should be mentioned that by the hydroxy styrenes resin that obtains of the polymerization of polyhydroxy styrene for example, the hydroxystyrene/methyl methacrylate multipolymer, hydroxy styrenes/cyclohexyl methacrylate multipolymer, hydroxy styrenes/styrol copolymer, hydroxy styrenes/alkoxystyrene multipolymer etc.In addition, can also use by at least a compound of phenol, cresols class and pyrocatechol and the novolac resin that one or more polycondensations that is selected from the compound of aldehydes and ketone obtain of being selected from.
When using above-mentioned polyphenolic compound (E), its content is generally 0.01～40 weight % based on the solids content of radiosensitive resin combination, is preferably 0.1～25 weight %.When polyphenolic compound (E) content was within above-mentioned scope, resolving power is tending towards improving and the visible transmission ratio is tending towards no longer reducing, and this is preferred.
As for linking agent (F), should be mentioned that methylol compound etc.
As for above-mentioned methylol compound, should be mentioned that the r-o-methylation resin, r-o-methylation melamine resin for example, r-o-methylation urea resin etc.Herein, as for the r-o-methylation melamine resin, should be mentioned that the methoxymethylation melamine resin, ethoxymethyl melamine resin, the third oxygen methylated melamines resin, fourth oxygen methylated melamines resin etc., and as for the r-o-methylation urea resin, should be mentioned that the methoxymethylation urea resin, the ethoxymethyl urea resin, third oxygen urea resin that methylates, the fourth oxygen urea resin etc. that methylates.Above-mentioned linking agent can use separately or two kinds or be used in combination more.
When using linking agent (F), its content is generally 0.01～15 weight % based on the solids content of radiosensitive resin combination, is preferably 1～10 weight %.When content of crosslinking agent was within above-mentioned scope, the visible transmission of resulting film had also improved than the performance of increase and hardening resin film, and this is preferred.
As for polymerisable monomer (G), should be mentioned that, for example, preferably should be mentioned that the polymerisable monomer that can carry out cationoid polymerisation by heating polymerisable monomer that can carry out radical polymerization and the polymerisable monomer that can carry out cationoid polymerisation etc.
As for the above-mentioned polymerisable monomer that can carry out radical polymerization, should be mentioned that, the compound that for example contains the polymerizable carbon-to-carbon unsaturated bond, can use the simple function group polymerisable monomer, also can use the polyfunctional group polymerisable monomer, for example bifunctional polymerisable monomer or trifunctional or more polyfunctional group polymerisable monomer etc.
The example of simple function group polymerisable monomer comprises nonyl phenyl Trivalin SF acrylate, nonyl phenyl Trivalin SF methacrylic ester, 2-hydroxyl-3-benzene oxygen propyl group acrylate, 2-hydroxyl-3-benzene oxygen propyl methyl acid esters, 2-ethylhexyl Trivalin SF acrylate, 2-ethylhexyl Trivalin SF methacrylic ester, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, N-V-Pyrol RC etc.
The example of bifunctional polymerisable monomer comprises 1,6 hexanediol diacrylate, 1, the 6-hexanediol dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, two (acrylyl oxy-ethyl) ethers of dihydroxyphenyl propane, 3-methyl pentanediol diacrylate, 3-methyl pentanediol dimethacrylate etc.
Trifunctional or more the example of polyfunctional group polymerisable monomer comprise Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate, tetramethylolmethane five acrylate, tetramethylolmethane pentamethyl-acrylate, dipentaerythritol acrylate, Dipentaerythritol hexamethyl acrylate etc.
In the above-mentioned polymerisable monomer, preferably use bifunctional or trifunctional or more multi-functional polymerisable monomer.Particularly, preferred tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc., more preferably dipentaerythritol acrylate.Also allow bifunctional or trifunctional or more multi-functional polymerisable monomer and simple function group polymerisable monomer are used in combination.
Polymerisable monomer as for carrying out cationoid polymerisation should be mentioned that, for example contains the polymerisable monomer of cationoid polymerisation functional group such as vinyl ether group, propenyl ether, epoxy group(ing), oxetanyl etc.The specific examples that contains the compound of vinyl ether group comprises triethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl etc.The specific examples that contains the compound of propenyl ether comprises 4-(1-propenyloxy group methyl)-1,3-dioxolane-2-ketone etc.The specific examples that contains the compound of epoxy group(ing) comprises bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic ring epoxy resins.The specific examples that contains the compound of oxetanyl comprises two { 3-(3-ethyl oxetanyl) methyl } ethers, 1, two { 3-(the 3-ethyl oxetanyl) methoxyl group } benzene of 4-, 1, two { 3-(the 3-ethyl oxetanyl) methoxyl group } methylbenzene of 4-, 1, two { 3-(the 3-ethyl oxetanyl) methoxyl group } hexanaphthenes of 4-, 1, two { 3-(the 3-ethyl oxetanyl) methoxyl group } methylcyclohexanes of 4-, 3-(3-ethyl oxetanyl) methylates novolac resin etc.
When using above-mentioned polymerisable monomer (G), independent or two or more being used in combination.The content of polymerisable monomer (G) based on the solids content of radiosensitive resin combination, is generally 0.1～20 weight %.
The example of above-mentioned silane coupling agent (H) comprises methyltrimethoxy silane, Union carbide A-162, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl three (2-methoxyethoxy) silane, 3-chloropropyl-Trimethoxy silane, 3-chloropropyl methyl-dichlorosilane, 3-chloropropyl methyl-dimethoxy silane, 3-chloropropyl methyl-diethoxy silane, 3-glycidoxypropyl-Trimethoxy silane, 3-glycidoxypropyl-triethoxyl silane, 3-glycidoxypropyl methyl-dimethoxy silane, 3-sulfydryl propyl group-Trimethoxy silane, 3-methacryloxypropyl-Trimethoxy silane, 3-methacryloxypropyl methyl-dimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-2-(N-vinyl benzyl amino-ethyl)-3-aminopropyl-Trimethoxy silane hydrochloride, hexamethyldisilazane, diamino silanes, triamino propyl group-Trimethoxy silane, 3-aminopropyl-Trimethoxy silane, 3-aminopropyl-triethoxyl silane, 3-aminopropyl methyl-diethoxy silane, 3-aminopropyl-three (2-methoxyethoxy) silane, 3-(2-amino-ethyl)-3-aminopropyl-Trimethoxy silane, 3-(2-amino-ethyl)-3-aminopropyl methyl-dimethoxy silane, 3-uride propyl group-Trimethoxy silane, 3-uride propyl group-triethoxyl silane, N-amino-ethyl-3-aminopropyl-Trimethoxy silane, N-amino-ethyl-3-aminopropyl methyl-dimethoxy silane, N-methyl-3-aminopropyl-Trimethoxy silane, N-phenyl-3-aminopropyl-Trimethoxy silane etc.
In the middle of them, preferably use the silane coupling agent that in its structure, contains epoxy group(ing).As for the above-mentioned silane coupling agent that in its structure, contains epoxy group(ing), should be mentioned that, 3-glycidoxypropyl-Trimethoxy silane for example, 3-glycidoxypropyl-triethoxyl silane, 3-glycidoxypropyl methyl-dimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc., more preferably should be mentioned that the silane coupling agent that contains the alicyclic epoxy base, for example 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
The content of silane coupling agent (H) based on radiosensitive resin combination, is preferably 0.01～10 weight %, 0.1～2 weight % more preferably, also 0.2～1 weight % more preferably.The content of preferred silane coupling agent is in above-mentioned scope, when using radiation-sensitive resin composition of the present invention to form the hardened resin pattern, transparency is tending towards improving because the visible transmission ratio of hardening resin pattern has increased, in addition, the tight adhesion of hardening resin pattern and base material also improves.
Preferably allow radiosensitive resin combination of the present invention comprise at least a tensio-active agent that is selected from siloxanes tensio-active agent, fluorine based surfactant and contains the siloxanes tensio-active agent of fluorine atom.
Above-mentioned siloxanes tensio-active agent comprises trade(brand)name: Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA and SH30PA (Toray SiliconeK.K. manufacturing); Trade(brand)name: polyether-modified silicone oil SH8400 (Toray Silicone K.K. manufacturing); Trade(brand)name: KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (Shin-EtsuSilicone K.K. manufacturing); Trade(brand)name: TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (GE Toshiba SiliconeK.K. manufacturing) etc.
Above-mentioned fluorine based surfactant comprises Florad FC430 and FC431 (Sumitomo 3M manufacturing); Megafack (trade(brand)name) F142D, F171, F172, F173, F177, F183 and R30 (Dainippon Ink ﹠amp; Chemicals Inc. makes); Eftop (trade(brand)name) EF301, EF303, EF351 and EF352 (shin Akita Kasei K.K. manufacturing); Surfron (trade(brand)name) S381, S382, SC101 and SC 105 (Asahi Glass Co., Ltd. makes); Trade(brand)name: E5844 (Daikin Fine ChemicalLaboratory K.K. manufacturing); Trade(brand)name: BM-1000 and BM-1100 (BM Chemie manufacturing) etc.
The above-mentioned siloxanes tensio-active agent that contains fluorine atom comprises Megafack (trade(brand)name) R08, BL20, F475, F477 and F443 (Dainippon ink; Chemicals Inc. makes) etc.
These tensio-active agents can use separately or two or more being used in combination.
In addition, in radiosensitive resin combination of the present invention, can also use other tensio-active agent together, for example acrylic polymers (acryl polymer) based surfactants and vinyl polymer based surfactants etc.
Acrylic polymer-based tensio-active agent comprises Disperon (trade(brand)name) OX-880, OX-881, OX883, OX-70, OX-77, OX-77HF, 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 (KusumotoChemicals manufacturing); Trade(brand)name: BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, EYK-361 and BYK-390 (HYK Chemie Japan manufacturing); Efka (trade(brand)name) LP3778 (Efka Chemicals manufacturing) etc.
The vinyl polymer based surfactants comprises Disperon (trade(brand)name) 1922,1927,1950,1951, P-410, P-410HF, P-420, P-425, PD-7 and LHP-90 (KusumotoChemicals manufacturing) etc.
If desired, radiosensitive resin combination of the present invention can also comprise other components, for example, and various additives such as antioxidant, dissolution inhibitor, sensitizing agent, UV light absorber, optical stabilization agent, adhesion activator, electron donor(ED) etc.
Radiosensitive resin combination of the present invention can prepare with the following method: will have indurative alkali soluble resins (A) and be dissolved in solution that obtains in the solvent (C) and the solution mixing that quinone di-azido compound (B) is dissolved in acquisition in the solvent (C).After the mixing, can add solvent (C) again.In addition, preferably after solution mixes, by the solids removed by filtration component, for example, preferably use strainer to filter, the aperture of filter device therefor is 3 μ m or following, is preferably more than to equal 0.1 μ m and smaller or equal to 2 μ m.The above-mentioned solvent that is used for each component can be identical, also can be different, and precondition is that they are compatible.
When the velocity of evaporation of n-butyl acetate was made as 1.0, the velocity of evaporation of radiosensitive resin combination (velocity of evaporation relatively) was preferably 0.10 to 0.16.If the relative velocity of evaporation of radiosensitive resin combination is within above-mentioned scope, then the nozzle of apparatus for coating is difficult for stopping up, and therefore is not easy to produce foreign matter, and need not be time-consuming for the dried floral of wet coating, thereby can boost productivity, be preferred mode.
When using radiosensitive resin combination to form the hardening resin pattern, when for example on substrate, forming the film of making by radiosensitive resin combination, above-mentioned film is exposed with radiation irradiation by mask, then, the acquisition resin pattern develops, this resin pattern is heat-treated, obtain the hardened resin pattern.
As for substrate, should be mentioned that, for example transparency glass plate etc.On above-mentioned substrate, can form TFT or be used for the circuit of CCD etc., colour filter etc.
Can be coated with method with the seam of rotary substrate not and form the film of making by radiosensitive resin combination.The application apparatus that is used to stitch the method for being coated with comprises that for example, seam is coated with machine, die coater, curtain stream coating machine etc.
After using, use together by heat drying (preliminary drying), vacuum-drying or dual mode, the evaporating volatile component, for example solvent etc. forms the radiosensitive resin combination film with low solvent.The thickness of radiosensitive resin combination film is generally 1.5～5 μ m.
Then, pass through the radiosensitive resin combination film of mask irradiation with radiation.The pattern of mask is suitably to select according to the hardening resin pattern of wanting.As for radiation, for example, use light beam such as g-line, i-line etc.Preferred mask calibrator, the steppers etc. of using carry out radiation irradiation.
After with radiation irradiation, with radiosensitive resin combination film development.Can develop like this, for example, the radiosensitive resin combination film after the exposure be contacted with photographic developer etc.
As for photographic developer, use alkaline aqueous solution usually.As for alkaline aqueous solution, use be the aqueous solution of basic cpd, basic cpd can be an inorganic alkaline compound, also can be organic basic compound.
The example of inorganic alkaline compound comprises sodium hydroxide, potassium hydroxide, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, Secondary ammonium phosphate, primary ammonium phosphate, potassium primary phosphate, water glass, potassium silicate, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, Sodium Tetraborate, potassium borate, ammoniacal liquor etc.
The example of organic basic compound comprises tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethyl ammonium, Monomethylamine, dimethylamine, Trimethylamine 99, monoethylamine, diethylamine, triethylamine, monoisopropylamine, Diisopropylamine, thanomin etc.Above-mentioned basic cpd is to use separately or two or more being used in combination.
In photographic developer, the consumption of basic cpd based on 100 weight part photographic developers, is generally 0.01～10 weight part, is preferably 0.1～5 weight part.
Photographic developer can also comprise tensio-active agent.The example of tensio-active agent comprises nonionogenic tenside, cats product, anion surfactant etc.
The example of nonionogenic tenside comprises polyoxyethylene deriv, Voranol EP 2001 for example, the polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ether etc., and ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty(acid)ester, the polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
The example of cats product comprises for example stearyl amine hydrochloride etc. of amine salt, and quaternary ammonium salt is Trimethyllaurylammonium chloride etc. for example.
The example of anion surfactant comprises for example sodium laurylsulfate of higher alcohol sulfate, oleyl alcohol sodium sulfate etc., alkyl-sulphate is sodium lauryl sulphate for example, ammonium lauryl sulfate etc., alkylaryl sulphonate is Sodium dodecylbenzene sulfonate for example, dodecyl sodium naphthalene sulfonate etc.
These tensio-active agents can use separately or two kinds or be used in combination more.
Photographic developer can comprise organic solvent.As for above-mentioned organic solvent, should be mentioned that water-miscible organic solvent such as methyl alcohol, ethanol etc.
As for the contact method of radiosensitive resin combination film and photographic developer, for example, can be immersed in the photographic developer being formed on on-chip radiosensitive resin combination film.By developing, be dissolved in the photographic developer by the irradiated radiation irradiated site of radiation in the exposure formerly of radiosensitive resin combination film, and the non-irradiated site of process radiation irradiation does not still keep, and is not dissolved in the photographic developer, thereby forms resin pattern.
For radiosensitive resin combination that the present invention comprises quinone di-azido compound (B),, also can easily dissolve and remove the radiation irradiated site even radiosensitive resin combination film only contacts the very short time with photographic developer.Same because comprise quinone di-azido compound (B), even radiosensitive resin combination film and photographic developer Long contact time, non-radiative line irradiated site does not dissolve yet and disappears.
After alkali develops, usually film is washed with water and drying.After the drying, with resulting resin pattern surface portion or all further use radiation irradiation.As for radiation source, preferably use uv irradiation line or deep ultraviolet radiation, and the irradiation of preferred per unit area is greater than the irradiation of above-mentioned radiation.
From considerations such as the thermotolerance of improving resulting hardening resin pattern, solvent resistances, preferably the resin pattern that will form like this carries out further thermal treatment (back baking).Heating adopts following method to carry out: with heating instrument for example hot-plate, clean stove (clean oven) etc., whole surface or its part of the substrate behind the radiation irradiation heated.Heating temperature is generally 150 ℃～250 ℃, is preferably 180 ℃～240 ℃.Be generally 5 minutes heat-up time～120 minutes, be preferably 15 minutes～90 minutes.By heating, the pattern sclerosis forms the hardened resin pattern.
The hardening resin pattern that uses the radiosensitive resin combination of the present invention to form in the above described manner is suitable as the hardening resin pattern that constitutes the TFT substrate, and the insulating film of organic EL, camera apparatus be the protective membrane of CCD for example, the display equipment of liquid-crystal display.
Embodiment
The present invention will be described in more detail based on embodiment, but needless to say, scope of the present invention is not limited to these embodiment.
Synthetic embodiment 1
The following monomer of in the 300mL four-hole boiling flask that has been equipped with agitator, cooling tube and thermometer, packing into, the 116g ethyl lactate is as solvent and 2.2g azobis isobutyronitrile, then under nitrogen gas stream, by stirring with these compound reactions 3 hours, internal temperature is remained on 100～110 ℃ simultaneously, obtain Resin A 1 solution.Resulting Resin A 1 is 8,300 based on the weight-average molecular weight of polystyrene calibration standards.
Methacrylic acid 10.8g
3-ethyl-3-methacryloxypropyl methyl trimethylene oxide 36.9g
N-cyclohexyl maleimide 31.4g
The measuring condition of above-mentioned weight-average molecular weight based on polystyrene calibration standards is described below.
Instrument: HLC-8120GPC (Tosoh Corp. manufacturing)
Pillar: TSK-GELG4000HXL+TSK-GELG2000HXL series connection
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran (THF) (THF)
Flow velocity: 1.0ml/min
Injection volume: 50 μ l
Monitor: RI
Measure sample concentration: 0.6 weight % (solvent: THF)
Calibration standard material: TSK STANDARD POLYSTYRENE:F-40, F-4, F-1, A-2500, A-500 (Tosoh Corp. manufacturing)
Embodiment 1
Following component is mixed down at 23 ℃, is that the tetrafluoroethylene cartridge filter of 1.0 μ m is depressed filtration adding by the aperture then, obtains radiosensitive resin combination filtrate.The solvent strength of this radiation-sensitive resin composition (C) is 84.9%.
The solution that comprises Resin A 1: 250 weight parts
(with solid content meter: 100 weight parts)
The compound of general formula (2): 20 weight parts
Adeka Optomer SP-172 (optics cationic polymerisation catalyst; Asahi Denka KogyoK.K. makes): 2 weight parts
Sun Aid SI-100L (hot cationic polymerisation catalyst; Sanshin Kagaku Kogyo K.K. makes):
2 weight parts
KBM-303 (silane coupling agent: β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; Shin-Etsu Chemical Co., Ltd. makes): 3 weight parts
Dipropylene glycol dimethyl ether (general formula (1) compound): 554 weight parts
(wherein, Q 4The substituting group of expression general formula (2-1))
Figure A20051008492700242
Said composition is illustrated in the table 1.
Comparative example 1
Adopt and obtain radiosensitive resin combination with embodiment 1 identical mode, difference is to use ethyl lactate to replace the dipropylene glycol dimethyl ether.The solvent of radiosensitive resin combination (C) concentration is 84.9%, and said composition is illustrated in the table 1.
Synthetic embodiment 2
Adopt and react with synthetic embodiment 1 identical mode, difference is to use 36g ethyl lactate and 146g 3-ethoxyl ethyl propionate as solvent, obtains Resin A 2 solution.Resulting Resin A 2 is 7,900 based on the weight-average molecular weight of polystyrene calibration standards.
Embodiment 2
Following component is mixed down at 23 ℃, is that the tetrafluoroethylene cartridge filter of 1.0 μ m is depressed filtration adding by the aperture then, obtains radiosensitive resin combination filtrate.The solvent of this radiosensitive resin combination (C) concentration is 84.9%.
The solution that comprises Resin A 2: 333 weight parts
(with solid content meter: 100 weight parts)
The compound of general formula (2): 20 weight parts
Adeka Optomer SP-172 (optics cationic polymerisation catalyst; Asahi Denka KogyoK.K. makes): 2 weight parts
Sun Aid SI-100L (hot cationic polymerisation catalyst; Sanshin Kagaku Kogyo K.K. makes):
2 weight parts
KBM-303 (silane coupling agent: β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; Shin-Etsu Chemical Co., Ltd. makes): 3 weight parts
Dipropylene glycol dimethyl ether (general formula (1) compound): 468 weight parts
Said composition is illustrated in the table 2.
Comparative example 2
Adopt and obtain radiation-sensitive resin composition with embodiment 2 identical modes, difference is to use ethyl lactate to replace the dipropylene glycol dimethyl ether.The solvent of radiation-sensitive resin composition (C) concentration is 84.9%, and said composition is illustrated in the table 2.
＜viscosity measurement embodiment 〉
Use viscometer (TV-30L type viscometer (No. 1 rotor); Toki Sangyo K.K. makes).Measuring result is presented in table 1 and 2.
＜mobile the embodiment that measures 〉
With the radiosensitive resin combination that obtains in 10 μ l embodiment and the comparative example with the pasteur volumetric pipette (5-3/4 "; Fischer Co. manufacturing) drips to SUS (stainless steel) 630 plates (size: 100mm * 200mm * 10mm, surfaceness: be equivalent to the direction microgroove finishing (one-direction hair line finishing) of JIS B0659 12.5-S), after dripping off, immediately SUS 630 plates are vertically placed.The microgroove of plate is perpendicular to the flow direction of composition (liquid).
Mobile distance when the resin combination of measuring radiation sensitivity stops to flow.The result is presented in table 1 and 2.
Mobile appraisal procedure is as follows.When track to being bent into of microgroove direction flow distance 5% or more for a long time, this situation is chosen as *, when track to the bending of microgroove direction less than the distance that flows 5% the time, this situation is chosen as zero.Assessment result is presented in table 1 and 2.
Table 1
Embodiment 1 Comparative example 1
Batching quantity The solution that comprises Resin A 1 250 250
General formula (2) compound 20 20
SP-172 2 2
SI-100L 2 2
KBM-303 3 3
The dipropylene glycol dimethyl ether 554 -
Ethyl lactate - 554
Quantity in solid ingredient Resin A 1 100 100
General formula (2) compound 20 20
SP-172 2 2
SI-100L 2 2
KBM-303 3 3
The dipropylene glycol dimethyl ether 554 -
Ethyl lactate - 704
Solvent ratio The dipropylene glycol dimethyl ether 78.7％ 0.0％
Ethyl lactate 21.3％ 100.0％
Amount of solvents 84.9％ 84.9％
Viscosity (mPa·s) 4.06 8.33
Distance flows (mm) 144 82
Mobile ○ ×
Table 2
Embodiment 2 Comparative example 2
Batching quantity The solution that comprises Resin A 1 333 333
General formula (2) compound 20 20
SP-172 2 2
SI-100L 2 2
KBM-303 3 3
The dipropylene glycol dimethyl ether 468 -
Ethyl lactate - 468
Quantity in solid ingredient Resin A 1 100 100
General formula (2) compound 20 20
SP-172 2 2
SI-100L 2 2
KBM-303 3 3
The dipropylene glycol dimethyl ether 554 -
Ethyl lactate 47 515
The 3-ethoxyl ethyl propionate 187 187
Solvent ratio The dipropylene glycol dimethyl ether 66.7％ 0.0％
Ethyl lactate 6.7％ 73.4％
The 3-ethoxyl ethyl propionate 26.6％ 26.6％
Amount of solvents 84.9％ 84.9％
Viscosity (mPa·s) 3.56 6.41
Distance flows (mm) 150 118
Mobile ○ ×
According to the present invention, can provide a kind of has excellent wetting property and stitches radiosensitive resin combination that can improve coating performance when being coated with machine when using stainless steel substrate.
Can use radiosensitive resin combination of the present invention to be formed for the insulating film that uses in the TFT type liquid-crystal display or every tabula rasa (photo spacer); the diffusion reflector that uses in the reflection-type TFT substrate; the projection that liquid crystal aligning is used, organic EL insulating film, CCD protective membrane etc.

Claims (11)

1, a kind of radiosensitive resin combination, said composition comprises (A) and has indurative alkali soluble resins, (B) quinone di-azido compound and (C) solvent, wherein solvent (C) contains the compound and the lactic acid alkyl ester of general formula (1),
R 1-O-[CH(CH 3)CH 2O] n-R 2 (1)
[in the general formula (1), R 1And R 2Expression contains the alkyl of 1～4 carbon atom independently, and n represents 1～4 integer.]
2, the composition of claim 1, wherein R 1And R 2Represent methyl or ethyl independently.
3, claim 1 or 2 composition, wherein n represents integer 2 or 3.
4, any one composition of claim 1～3, wherein the content of solvent (C) is 75%～88 weight % based on the total amount of radiosensitive resin combination.
5, any one composition of claim 1～4, the content of the compound of its formula of (1) is 50～99 weight % based on the solvent total amount.
6, any one composition of claim 1～5, wherein the content of lactic acid alkyl ester is 1～50 weight % based on the solvent total amount.
7, any one composition of claim 1～6, the alkali soluble resins (A) that wherein has sclerosis character is a kind of multipolymer, this multipolymer comprise derived from unsaturated carboxylic acid component units (a1) and derived from the component units (a2) of the unsaturated compound (except the unsaturated carboxylic acid) that contains sclerosis base.
8, the composition of claim 7, wherein in the component units (a2) derived from the unsaturated compound (except the unsaturated carboxylic acid) that contains the sclerosis base, the sclerosis base is an oxetanyl.
9, any one composition of claim 1～8, the alkali soluble resins (A) that wherein has sclerosis character is the multipolymer that also comprises at least a component units (a3), and described component units (a3) is selected from: the component units (a34) that obtains derived from the component units (a31) of the carboxylicesters that contains olefinic double bond, derived from the component units (a33) of the component units (a32) of the aromatic ethenyl compound that contains the polymerizable carbon-to-carbon unsaturated bond, derived from ethylene base cyanogen compound and the unsaturated link(age) fracture by N-substituted maleimide amine compound.
10, a kind of hardening resin pattern that forms by any one composition of claim 1～9.
11, a kind of indicating meter that comprises the hardening resin pattern of claim 10.
CNA2005100849279A 2004-07-28 2005-07-25 Radiation sensitive resin composition Pending CN1903942A (en)

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