WO2007125818A1 - 重合体及びそれを含有する感光性樹脂組成物 - Google Patents
重合体及びそれを含有する感光性樹脂組成物 Download PDFInfo
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- WO2007125818A1 WO2007125818A1 PCT/JP2007/058551 JP2007058551W WO2007125818A1 WO 2007125818 A1 WO2007125818 A1 WO 2007125818A1 JP 2007058551 W JP2007058551 W JP 2007058551W WO 2007125818 A1 WO2007125818 A1 WO 2007125818A1
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
Definitions
- the present invention relates to a ring-closed polyimide polymer used for an interlayer insulating film (passivation film), a surface protective film (overcoat film), an insulating film for a high-density mounting substrate, and the like of a semiconductor element, and It is related with the photosensitive resin composition to contain. More specifically, the present invention is capable of high-thickness coating and alkali development that are highly soluble in common solvents, and can obtain a cured product with high resolution.
- the present invention relates to a ring-closed polyimide polymer suitable for use in a film and an insulating film for a high-density mounting substrate, and a photosensitive resin composition containing the polymer.
- polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used for surface protective films, interlayer insulating films, and the like used in semiconductor elements of electronic devices.
- various photosensitive polyimide resins that have been given photosensitivity to improve film formation accuracy due to high integration of semiconductor elements have been proposed, and side-chain polymerizable negative photosensitive polyimide is widely used. .
- Patent Document 1 discloses a photosensitive composition using an aromatic polyimide precursor having an acrylic side chain.
- this photosensitive composition has a problem that it is difficult to cope with a high film thickness due to the problem of light transmittance, and the residual stress after curing is large.
- Patent Documents 2 and 3 propose positive photosensitive polyimide compositions that can be alkali-developed.
- the applicability of these photosensitive polyimide compositions is not always good, and it has been difficult to cope with a high film thickness of, for example, 15 / m or more.
- a high film thickness of, for example, 15 / m or more.
- high film thickness coating and high resolution There was a problem that it was difficult to meet the required surface protective film, interlayer insulating film and insulating film application for high-density mounting substrates.
- Many other patents have been filed, but it is difficult to sufficiently satisfy the required characteristics due to the high integration and thinning of semiconductor elements.
- Patent Document 1 Japanese Patent Application Laid-Open No. 63-125510
- Patent Document 2 Japanese Patent Laid-Open No. 3-204649
- Patent Document 3 Japanese Patent Laid-Open No. 3-209478
- the present invention has been made in view of the above-described problems of the prior art, and the problem is that high-thickness coating and alkali development with high solubility in general solvents are required.
- a ring-closed polyimide polymer suitable for surface protection films, interlayer insulation films, and insulation films for high-density mounting substrates capable of obtaining a cured product with high resolution, and a photosensitive material containing the same It is in providing a conductive resin composition.
- a polymer comprising a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (3).
- X represents a tetravalent aromatic or aliphatic hydrocarbon group
- A represents a divalent group represented by the following general formula (2)
- R 1 represents a divalent group
- R 2 independently represents a hydrogen atom, an acylol group, or an alkyl group
- n 1 and n 2 are integers of 0 to 2
- at least one of n 1 and n 2 is 1 or more, and at least one of R 2 is a hydrogen atom
- X represents a tetravalent aromatic or aliphatic hydrocarbon group
- B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following general formula (4). Represents a divalent group
- Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms
- a photosensitive resin composition comprising (A) the polymer according to [1] or [2], (B) a photoacid generator, and (C) a crosslinking agent.
- novel ring-closed polyimide polymer of the present invention and the photosensitive resin composition containing the polymer are capable of high film thickness coating and alkali development with high solubility in general solvents, It is possible to obtain a cured product with high resolution, surface protection film, interlayer insulation This is advantageous in that it is suitable for a film and an insulating film application for a high-density mounting substrate.
- FIG. 1 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention.
- FIG. 2 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention.
- the polymer (A) of the present invention comprises a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (3). The details will be described below.
- X in the general formula (1) is a tetravalent aromatic hydrocarbon group or a tetravalent aliphatic hydrocarbon group, preferably a tetravalent aliphatic hydrocarbon group.
- tetravalent aromatic hydrocarbon group it is possible to enumerate a tetravalent group in which four hydrogens in the aromatic hydrocarbon mother skeleton are substituted.
- aromatic hydrocarbon group examples include the following groups.
- Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, a tetravalent group in which four hydrogens in the base skeleton of a chain hydrocarbon group, an alicyclic hydrocarbon, or an alkyl alicyclic hydrocarbon are substituted can be given. These tetravalent aliphatic hydrocarbon groups may include an aromatic ring in at least a part of the structure.
- examples of the chain hydrocarbon include ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, and n-dodecane.
- the alicyclic hydrocarbon specifically, it is possible to enumerate a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or higher hydrocarbon, and the like.
- Examples of monocyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, and cyclooctane.
- Bicyclic hydrocarbons include bicyclo [2.2.1] heptane, bicyclo [3.1.1] heptane, bicyclo [3.1.1] hept_2_en, bicyclo [2. 2. 2] Octane, bicyclo [2.2.2] Oct 7-en.
- Tricyclic or higher hydrocarbons include tricyclo
- alkyl alicyclic hydrocarbon examples include those obtained by substituting the alicyclic hydrocarbon with an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group. More specifically, methylcyclopentane, 3-ethyl-1-methyl-1-cyclohexene, 3-ethyl-1-cyclohexene and the like can be mentioned.
- a tetravalent aliphatic hydrocarbon group containing an aromatic ring in at least a part of its structure the number of aromatic rings contained in one molecule is 3 or less. It is especially preferred that it is the one that I like . More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene and the like can be mentioned.
- Preferred tetravalent group nucleus as X includes n-butane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [2.2.2] Okuto _ 7 _ E down, tetracyclo [6. 2. 1. I 3 '6 . 0 2' 7] dodecane, can be exemplified Mechirushikurobe lanthanum like.
- a in the general formula (1) is a divalent group represented by the general formula (2).
- R 1 is a divalent group. Specific examples of R 1 include an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, an alkylene group (excluding a methylene group), a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. it can.
- R 2 independently represents a hydrogen atom, an acyl group or an alkyl group.
- Preferred examples of the acyl group include a formyl group, a acetyl group, a propionyl group, a butyroyl group, and an isobutyroyl group.
- Preferred examples of the alkyl group include a methylol group, an ethyl group, an n-propyl group, and an isopropyl group. N_butyl group, n-pentyl group, n_hexynole group, n-octyl group, n-decyl group, n-dodecyl group and the like. Note that at least one of R 2 is a hydrogen atom.
- n 1 and n 2 are integers of 0 to 2 , and at least one of n 1 and n 2 is 1 or more.
- X in the general formula (3) is a tetravalent aromatic hydrocarbon group or a tetravalent aliphatic hydrocarbon group.
- X in the general formula (3) is the same as X in the general formula (1), and the same examples can be given as preferred examples.
- B in the general formula (3) is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a divalent group represented by the general formula (4).
- C2-C20 substituted or unsubstituted key Specifically, the alkylene group is preferably an alkylene group having 4 or more carbon atoms. Examples of the alkylene group having 4 or more carbon atoms include an alkylene group having 4 carbon atoms such as 1,4-butylene group; an alkylene group having 5 carbon atoms such as 1,5-pentylene group; 2-methyl-1,5-pepe.
- alkylene groups having 6 carbon atoms such as an nylene group and 1,6_hexylene group
- alkylene groups having 7 to 20 carbon atoms such as 1,10-decylene group and 1,12-dodecylene group.
- an alkylene group having 6 or more carbon atoms is preferable, and an alkylene group having 7 to 20 carbon atoms is more preferable, because the solubility of the polymer in a solvent is improved.
- Z in the general formula (4) is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.
- the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 3 or more carbon atoms.
- the alkylene group having 3 or more carbon atoms include alkylene having 3 to 5 carbon atoms such as 1,3_propylene group, 2,2-dimethylpropylene group, 1,4-butylene group, 1,5_pentylene group and the like.
- the divalent group represented by the general formula (4) is more preferably
- the polymer is usually a monomer represented by the following general formula (5) (hereinafter, also referred to as “monomer (5)”), a monomer represented by the following general formula (6) (hereinafter, “ Monomer (6) ”) and a monomer represented by the following general formula (7) (hereinafter also referred to as“ monomer (7) ”) in a polymerization solvent to synthesize polyamic acid, and further imide It can be obtained by performing a chemical reaction.
- the following two methods are known as procedures for synthesizing polyamic acid, and they may be synthesized by any method.
- X in the general formula (5) is the same as X in the general formula (1), and the general formula (
- R 2, n ⁇ and n 2 in the general formula (2) is the same as R 2, n ⁇ and n 2, B in the general formula (7), the general Same as B in formula (3).
- non-protonic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolatatane, dimethylsulfoxide, etc .
- protic solvents are used.
- the imidization reaction a heat imidization reaction and a chemical imidation reaction are generally known, but it is preferable to synthesize the polymer (A) by a heat imidization reaction.
- the heating imidization reaction is usually carried out by heating the polyamic acid synthesis solution at 120 to 210 ° C.:! To 16 hours. If necessary, an azeotropic solvent such as toluene, xylene or the like may be used to remove the water in the system and perform a strong reaction.
- the (A) polymer weight average molecular weight (hereinafter also referred to as "Mw”) measured by gel permeation chromatography (GPC) is usually about 2,000 to 500,000. Yes, preferably about 3,000 to 200,000. If the Mw force is less than S2,000, sufficient mechanical properties as an insulating film tend not to be obtained. On the other hand, if Mw exceeds 500,000, the photosensitive resin composition obtained by using this (A) polymer tends to be poorly soluble in a solvent or a developer.
- Ratio of [0051] (A) of the polymer, the total monomer (monomer (5) + monomer (6) + monomer (7)) accounted mode Nomar (5) is usually 40 to 60 mol 0/0, preferably 45 to 55 mole 0/0. Power ratio of monomer (5) in the total monomers is less than 40 mole 0/0, or is 60 mole 0/0 greater, there is a tendency that the molecular weight of the resulting polymer (A) is lowered.
- the proportion of the monomer (6) and the monomer (7) Monomer (6) to the sum of, usually 10 to 99 mol 0/0, good Mashiku is 20 to 95 mole 0/0, more preferably is 30 to 90 mole 0/0.
- the photosensitive resin composition of the present invention contains the aforementioned (A) polymer, (B) a photoacid generator, and (C) a crosslinking agent. The details will be described below.
- the (B) photoacid generator contained in the photosensitive resin composition of the present invention is a compound that generates an acid upon irradiation with radiation (hereinafter also referred to as “exposure”).
- (B) photoacid generators having such properties include ododonium salt compounds, sulfoyuum salt compounds, sulfone compounds, sulfonic acid ester compounds, halogen-containing compounds, sulfonimide compounds, diazomethane compounds, and the like.
- photoacid generator of a chemical amplification system a naphthoquinonediazide (NQD) photoacid generator such as a diazoketone compound.
- Examples of the ododonium salt compounds include diphenyl trifluoromethyl sulfonate, diphenyl nitronafluorobutane sulfonate, diphenyl dimethylpyrene sulfonate, and diphenyl dimethyl sulfonate.
- sulfonium salt compounds include triphenyl sulfone trifluoromethane sulfonate, triphenyl sulfone nonafluorobutane sulfonate, triphenyl sulfone camphor sulfonate, triphenyl sulfone.
- Examples of the sulfone compound include ⁇ -ketosulfone, ⁇ sulfonylsulfone, and the like.
- Examples include a-diazo compounds. More specific examples include phenacyl phenyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like.
- Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. More specifically, benzoin tosylate, pyrogallol tristrifluormethane sulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl -9,10-diethoxyanthracene 1_sulfonate, monomethylol benzoin tosylate , Himeichiro Norevenzoin octane sulfonate, Hiichi methylol benzoin trifluoromethanesulfate Examples include phonate and a-methylol benzoindodecyl sulfonate.
- halogen-containing compound examples include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like.
- preferred halogen-containing compounds include 1,1-bis (4-chlorophenol) -1,2,2-trichloroethane, phenol-bis (trichloromethyl) _s-triazine, 4 —Methoxyphenyl monobis (trichloromethyl) _ s-triazine, styryl monobis (trichloromethyl) _ s-triazine, 4-methoxystyryl norbis (trichloromethyl) _ s-triazine, naphthyl monobis (trichloromethyl) _ s- Examples thereof include triazine and s-triazine derivatives represented by the following general formula (8).
- R 3 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms
- Y represents a halogen atom
- Q represents an oxygen atom. Or a sulfur atom.
- the s_triazine derivative represented by the general formula (8) has wide absorption in the g-line, h-line, and i-line regions, and generates a general radiation-sensitive acid having another triazine skeleton. As a result, it is possible to obtain an insulating cured product having higher acid generation efficiency and higher residual film ratio than the agent.
- the alkyl group having 1 to 4 carbon atoms represented by R 3 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, tert-butyl group and the like.
- alkoxy group having 1 to 4 carbon atoms examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and the like.
- R 3 in the general formula (8) is more preferably a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the halogen atom represented by Y is a fluorine atom, a chlorine atom, an odor More preferred is a chlorine atom, which is preferably an elementary atom or an iodine atom. Further, Q in the general formula (8) is more preferably an oxygen atom.
- S-triazine derivatives can be used singly or in combination of two or more.
- Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide. N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hepto-1-ene _ 2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, etc. Can do.
- diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane and bis.
- examples of the diazoketone compound include 1,3 diketoe 2 diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like.
- Specific examples of preferred diazoketone compounds include 1,2-naphthoquinone diazide 4 sulfonate compounds of phenols.
- sulfonium salt compounds sulfone compounds, halogen-containing compounds, diazoketone compounds, sulfonimide compounds, and diazomethane compounds are preferred. Sulfoyuum salt compounds and halogen-containing compounds are more preferred. .
- 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate 4,7 _di-n-butoxy 1 _naphthyltetrahydrothiophene nitrotrifluoromethane Phonate, 4,7-di-n-hydroxy-1-1-naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4,7 _di-n-butoxy 1 _naphthyltetrahydrothiohexafluorophosphate, 4 _n—Butoxy 1 _Naphthyltetrahydrothiooff Enum trifluoromethanesulfonate, 4-methoxyphenylbis (trichloromethyl) -s triazine, styryl monobis (trichloromethyl) s triazine, 4-methoxystyryl bis (trichloromethyl)
- the content ratio of (B) photoacid generator is as follows: (A) 100 parts by mass of polymer (provided that (A) other polymer other than the polymer is further contained, (A) )
- the polymer and other polymers in total (100 parts by mass) are usually from 0.:! To 20 parts by mass, preferably from 0.5 to 10 parts by mass. If the amount is less than 1 part by mass, it may be difficult to cause a chemical change due to the catalytic action of the acid generated by exposure. On the other hand, if it exceeds 20 parts by mass, there is a possibility that uneven coating may occur when the photosensitive resin composition is applied, or insulation after curing may be deteriorated.
- the crosslinking agent is a compound that forms a bond with a compounded composition such as a resin or other crosslinking agent molecules by the action of heat or acid.
- a compounded composition such as a resin or other crosslinking agent molecules by the action of heat or acid.
- Specific examples of the (C) crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, and compounds having an alkoxyalkylated amino group. Of these, compounds having an amino group which is alkoxyalkylated are preferred.
- these (C) crosslinking agents can be used individually by 1 type or in combination of 2 or more types.
- Examples of the polyfunctional (meth) atalyte toy compound include trimethylolpropane tri (meth) atelate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra.
- Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.
- Hydroxymethyl group-substituted phenolic compounds include 2-hydroxymethyl_4,6-dimethylphenol, 1,3,5_trihydroxymethylbenzene, 3,5-dihydroxymethyl_4-methoxytoluene [2, 6_ Bis (hydroxymethyl) _p_cresol] and the like.
- Examples of compounds having an alkoxyalkylated amino group include (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, and the like.
- the compound having an alkoxyalkylated amino group may be a mixture in which a plurality of substituted compounds are mixed, and some of them contain an oligomer component that is partially self-condensed. Can do.
- the compound represented by the formula (9) (hexakis (methoxymethyl) melamine) is commercially available under the trade name “Cymel 300” (manufactured by Cytec Industries).
- the compound represented by the formula (11) (tetrakis (butoxymethyl) glycoluril) is commercially available under the trade name “Cymel 1170” (manufactured by Cytec Industries).
- Compounds having an alkoxyalkylated amino group include hexakis (methoxymethyl) melamine (formula (9)), tetrakis (methoxymethyl) glycoluril (formula (12)), tetrakis (butoxy). Hexakis (methoxymethyl) melamine (formula (9)) is most preferred, with methyl) glycoluril (formula (11)) being particularly preferred.
- the content of the crosslinking agent is such that the film formed of the photosensitive resin composition is sufficiently hard.
- the amount is appropriately set so as to be an amount to be changed.
- the content ratio of (D) the crosslinking agent is (A) with respect to 100 parts by mass of the polymer (provided that (A) other polymer other than the polymer is further contained ( A) In general, it is 5 to 50 parts by mass, preferably 10 to 40 parts by mass, based on 100 parts by mass of the polymer and other polymers. If it is less than 5 parts by mass, the resulting insulating layer may have insufficient solvent resistance and plating solution resistance. On the other hand, if it exceeds 50 parts by mass, the developability of the thin film formed by the photosensitive resin composition may be insufficient.
- the photosensitive resin composition of the present invention can further contain other polymer (resin) other than the above-mentioned (A) polymer, if necessary, within a range not impairing the effects of the present invention.
- the “other polymer (resin)” that can be contained is not particularly limited, but an alkali-soluble one is preferred, and an alkali-soluble resin having a phenolic hydroxyl group (hereinafter referred to as “phenol resin”). It is more preferable to contain (in order to improve resolution).
- phenol resin examples include novolak resin, polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol dimethyl ether condensed resin, crezo-loxylylene glycol dimethyl ether condensed resin, phenol-dicyclopentagen condensed resin. Examples thereof include resins.
- novolak resin examples include phenol / formaldehyde condensed novolak resin, talesol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.
- the novolac resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.
- phenols used in this case include phenol, o_cresol monole, m_creso mono nore, p_creso mono nore, o-ethino leuenore, m-ethino leuenol, p_ethyl phenol, o_Butylphenol, m_Butylphenol, p—Butylphenol, 2, 3_Xylenol, 2, 4_Xylenol, 2,5_Xylenol, 2, 6-Xylenol, 3, 4-Xylenol, 3, 5-Xylenol, 2, 3, 5— ⁇ Limethinophenol, 3, 4, 5_trimethylphenol, catechol, resorcinol, pyrogallo , ⁇ -naphthol, ⁇ -naphthol and the like. Examples of the phenols
- Monomers other than hydroxystyrene constituting the copolymer of polyhydroxystyrene are not particularly limited. Specifically, styrene, indene, ⁇ _methoxystyrene, ⁇ -butoxystyrene, ⁇ -acetoxystyrene , ⁇ -hydroxy styrene derivatives such as methylol styrene; (meth) acrylic acid, methylol (meth) acrylate, ethyl (meth) acrylate, ⁇ — propyl (meth) acrylate, isopropyl (meth) acrylate Rate, ⁇ _butyl (meth) acrylate, sec-butyl (meth) acrylate, t_butyl (meth) acrylate, etc .; (meth) acrylate, etc .; methyl butyl ether, ethyl butyl ether, n — Butyl vinyl vinyl
- the content ratio of the phenol resin is preferably 0 to 90 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the total of (A) the polymer and the phenol resin. It is particularly preferable to use 10 to 70 parts by mass. If the amount is less than 5 parts by mass, the effect of including this phenol resin tends to be difficult to be exhibited. On the other hand, if it exceeds 90 parts by mass, the mechanical strength of the film tends to decrease.
- the photosensitive resin composition of the present invention may contain a phenolic low molecular compound in addition to the above-mentioned phenol resin.
- phenolic low molecular weight compounds that can be contained include 4,4'-dihydroxydiphenylmethane, 4,4'dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1, 1 —Bis (4-hydroxyphenyl) 1- 1_phenenoreethane, tris (4-hydroxyphenyl) ethane, 1,3_bis [1- (4-hydroxyphenyl) -1-1-methylethyl] benzene, 1 , 4 _bis [1 _ (4 —hydroxyphenyl) 1 1-methylethyl] benzene, 4, 6 _bis [1— (4-hydroxyphenyl) _ 1 _methylethyl 3-dihydroxybenzene, 1, 1 _bis (4-Hydroxyphenyl) _ 1 _ [4—
- the content ratio of the phenolic low molecular weight compound is 100 parts by mass of (A) polymer (however, (A) When other polymer other than the polymer is further contained, it is preferable to set it to 0 to 100 parts by mass with respect to (A) the total of 100 parts by mass of the polymer and the other polymer):! It is more preferable to set it to ⁇ 60 parts by mass. Particularly preferable is 5 to 40 parts by mass. If the amount is less than 1 part by mass, the effect of containing this phenolic low molecular weight compound tends to be hardly exhibited. On the other hand, if it exceeds 100 parts by mass, the mechanical strength of the film tends to decrease.
- the organic resin in order to improve the handleability and to adjust the viscosity and storage stability, the organic resin is used as necessary within a range not impairing the effects of the present invention.
- the solvent can be contained.
- the type of solvent that can be contained is not particularly limited, but for example, aprotic such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl_2_pyrrolidone, ⁇ -butyrolatatone, dimethylsulfoxide, etc.
- Solvent phenolic protic solvents such as metataresole are preferably used.
- propylene glycol monoalkyl ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates instead of or together with the above solvents.
- Organic solvents such as alcohols, aliphatic alcohols, lactic acid esters, aliphatic carboxylic acid esters, alkoxy aliphatic sulfonic acid esters, and ketones.
- propylene glycol monoalkyl ethers examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.
- propylene glycol dialkyl ethers examples include propylene glycol jet nole etherate, propylene glycol nole propenolate nole, propylene glycol nole di ether ether and the like.
- propylene glycol monoalkyl ether acetates examples include propylene glycol monoremonomethinoatenoate acetate, propylene glycolenomonoethylenoatenoacetate, propylene glycolenomonopropinoreatenoacetate, propylene glycol Noremonobutyl ether acetate and the like.
- Aliphatic alcohols include 1-butanol, 2-butanol, 1_pentanol, 2_pentanol, 4_methyl_2_ Examples include pentanol and 1-hexanol.
- Examples of the lactic acid esters include methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate pills.
- Examples of aliphatic carboxylic acid esters include n- propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutinole propionate, etc. Can be mentioned.
- alkoxy aliphatic carboxylic acid esters examples include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3_ethoxypropionate, ethyl 3-ethoxypropionate, and the like.
- ketones examples include 2_heptanone, 3_heptanone, 4_heptanone, cyclopentanone, and cyclohexanone.
- ethyl acetate, 2_heptanone, cyclohexanone, propylene glycol mono-mono methino ethenore, propylene glycol mono meth- eno ethenore acetate, and butyl acetate are preferred.
- Monomethyl ether is particularly preferred.
- These solvents can be used alone or in combination of two or more. The solvent is usually used so that the total content of components other than the solvent is 1 to 60% by mass.
- the photosensitive resin composition of the present invention may contain other additives such as a basic compound, an adhesion aid, and a surfactant as necessary, as long as the effects of the present invention are not impaired. S can.
- Examples of the basic compound include triethylamine, tri_n-propylamine, tri_n-butynoleamine, tri_n-pentylamine, tri_n-hexylamine, tri_n-heptylamine, ⁇ n-n-tactileamine, ⁇ n-ninoreamine, Examples include trialkylamines such as ⁇ n_decinoreamine, ⁇ n-dodecylamine, and n-dodecyldimethylamine, and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine, and imidazole.
- the content of the basic compound is usually 5 parts by mass or less, preferably 3 parts by mass or less, with respect to 100 parts by mass of the (A) polymer.
- the basic compound content is 5 for (A) 100 parts by mass of the polymer. If the amount is more than part by mass, the photoacid generator may not function sufficiently.
- the photosensitive resin composition of the present invention may contain an adhesion assistant in order to improve adhesion to the substrate.
- a functional silane coupling agent is effective as the adhesion assistant.
- the functional silane coupling agent refers to a silane coupling agent having a reactive substituent such as a carbonyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Specific examples include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxylane, vinyltriacetoxysilane, butyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane. , ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
- the content of the adhesion aid is (
- the photosensitive resin composition of the present invention may contain a surfactant for the purpose of improving various properties such as coating properties, defoaming properties, and leveling properties.
- a surfactant for the purpose of improving various properties such as coating properties, defoaming properties, and leveling properties.
- the surfactant include ⁇ -1000, ⁇ -1100 (above, manufactured by Sakai Chemi Co., Ltd.), MegaFuck F142D, F172, F173, F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.) Fluorard FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3EM), Surflon S-112, S-113, S-131, S-141, S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, i-190, i-193, SZ-6032, SF-8428 (above, manufactured by Toray Dowko Silicone Co., Ltd.) Flu
- the photosensitive resin composition according to the embodiment of the present invention can be suitably used particularly as a surface protective film or an interlayer insulating film material of a semiconductor element.
- the photosensitive resin composition of the embodiment of the present invention is applied to a support (a copper foil with resin, a copper wafer with a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.) and dried to remove a solvent or the like. Volatilizes to form a coating film. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter referred to as “PEB”) is performed to promote the reaction between the phenol ring and the crosslinking agent. Then Al A desired pattern can be obtained by developing with a caustic developer and dissolving and removing unexposed areas. Furthermore, a cured film can be obtained by performing a heat treatment to develop the insulating film characteristics.
- PEB heat treatment
- a coating method such as a dubbing method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used.
- the coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution.
- a pre-beta treatment is usually performed to evaporate the solvent.
- the conditions vary depending on the composition of the photosensitive resin composition, the film thickness used, etc. Usually 70 to 150 ° C, preferably 80 to 140 ° C, and about! To 60 minutes.
- Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line, i-line and other ultraviolet rays, electron beams, and laser beams.
- Exposure light amount is suitably selected according to the light source and the resin film thickness and the like to be used, for example, when irradiated with ultraviolet rays from a high pressure mercury lamp, the resin film thickness 10 to 50 / m, usually, 100 ⁇ 5000mJ / cm 2 of about It is.
- PEB is performed to accelerate the curing reaction between the phenol ring and the (C) crosslinking agent by the generated acid.
- the PEB conditions vary depending on the composition of the photosensitive resin composition and the film thickness used, but are usually 70 to 150 ° C, preferably 80 to 140 ° C, and about! To 60 minutes. .
- development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method.
- the development conditions are usually 20 to 40 ° C: about 10 to 10 minutes.
- alkaline developer examples include alkaline compounds such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline, and the concentration is about 1 to 10% by mass.
- alkaline aqueous solution dissolved in water.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution.
- After developing with an alkaline developer wash with water and dry.
- the film can be sufficiently cured by heat treatment.
- the photosensitive resin composition is cured by heating at a temperature of 100 to 400 ° C for about 30 minutes to 10 hours. be able to.
- heating can be performed in multiple stages in order to sufficiently advance the curing or to prevent deformation of the obtained pattern shape. For example, when performing in two stages, the first stage is heated at a temperature of 50 to 200 ° C. for about 5 minutes to 2 hours, and further in the second stage at a temperature of 100 to 400 ° C. for 10 minutes to It can be hardened by heating for about 10 hours.
- a hot plate, oven, infrared furnace, microwave oven, or the like can be used as the heating equipment.
- a semiconductor device using the photosensitive resin composition of the embodiment of the present invention will be described with reference to the drawings.
- a patterned insulating film 3 is formed on a substrate 1 on which a patterned metal pad 2 is formed using the photosensitive resin composition of the present embodiment.
- the metal wiring 4 is formed so as to be connected to the metal pad 2, a semiconductor element can be obtained.
- a patterned insulating film 5 may be formed on the metal wiring 4 by using the photosensitive resin composition of the present embodiment.
- the photosensitive resin composition which is this embodiment is used, the semiconductor element which has the insulating resin layer formed of this photosensitive resin composition can be obtained.
- a photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C for 3 minutes to produce a uniform coating film having a thickness of 20 zm.
- a coating film with defects such as cracks was evaluated as “bad”, and a crack without defects such as cracks was determined as “good”.
- Araina (Suss Microtec Co. MA- 0.99) Rere use and the ultraviolet rays from a high-pressure mercury lamp through a putter Nmasuku, so that the amount of exposure at a wavelength of 350nm is 1000 ⁇ 5000mj / cm 2, coated test
- the coated wafer obtained in (1) was exposed. Subsequently, it was heated (PEB) at 110 ° C. for 3 minutes on a hot plate, and then dip-developed for 60 seconds at 23 ° C. using an aqueous 38 mass% tetramethylammonium hydroxide solution. The case where the pattern was formed according to the mask was “good”, and the case where the pattern was not formed according to the mask was “bad”.
- a polymer was obtained in the same manner as in Synthesis Example 1 except that each monomer and NMP were blended in the molar ratio shown in Table 1 and the mass shown in Table 2.
- Table 2 shows the yield (g) and molecular weight Mw of the obtained polymer.
- imide was confirmed by IR analysis that there is absorption of 1778cm _1 that shows.
- the structure of the monomer used in each synthesis example is shown below.
- a photosensitive resin composition (Example 1) was obtained by mixing 1.5 parts of an acid generator (B-1) and 15 parts of a crosslinking agent (C1). Evaluation of the mixing property of the obtained photosensitive resin composition was “good”, evaluation of coating property was “good”, and evaluation of patterning property was “good”.
- a photosensitive resin composition (Examples 2 to 11 and Comparative Example 1) was obtained in the same manner as in Example 1 except that the formulation shown in Table 3 was used.
- Table 4 shows the evaluation of the mixing property, coating property, and patterning property of the obtained photosensitive resin composition. The meanings of the abbreviations in Table 3 are as shown below.
- B-4 2- [2- (5-Methylfuran_2_yl) etul] -4, 6_bis (trichloromethylolene) -s-triazine (trade name: TME-triazine, manufactured by Sanwa Chemical Co., Ltd.)
- C— 2 Tetramethoxymethyl dalcoluril (Cytech Industries, trade name: Saimenole 1174)
- C-3 Product name: Epicoat (registered trademark) 828, manufactured by Japan Epoxy Resin Co., Ltd.
- the polymer of the present invention and the photosensitive resin composition containing the polymer are suitable for use as a surface protective film, an interlayer insulating film, and an insulating film for a high-density mounting substrate, and are extremely useful industrially.
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JP2008513168A JP5141552B2 (ja) | 2006-04-24 | 2007-04-19 | 重合体及びそれを含有する感光性樹脂組成物 |
KR1020087026896A KR101281965B1 (ko) | 2006-04-24 | 2007-04-19 | 중합체 및 이를 함유하는 감광성 수지 조성물 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008033159A (ja) * | 2006-07-31 | 2008-02-14 | Hitachi Chemical Dupont Microsystems Ltd | ネガ型感光性樹脂組成物、パターン硬化膜の製造方法および電子部品 |
JP2008083359A (ja) * | 2006-09-27 | 2008-04-10 | Jsr Corp | 感光性樹脂組成物及び硬化膜 |
USRE43372E1 (en) | 1999-03-05 | 2012-05-08 | Duke University | C16 unsaturated FP-selective prostaglandins analogs |
US8541466B2 (en) | 2000-03-31 | 2013-09-24 | Duke University | Compositions and methods for treating hair loss using non-naturally occurring prostaglandins |
US8618086B2 (en) | 2000-03-31 | 2013-12-31 | Duke University | Compositions and methods for treating hair loss using C16-C20 aromatic tetrahydro prostaglandins |
US8722739B2 (en) | 2008-10-29 | 2014-05-13 | Novaer Holdings, Inc. | Amino acid salts of prostaglandins |
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JPH03177430A (ja) * | 1989-12-06 | 1991-08-01 | Tomoegawa Paper Co Ltd | ポリアミドイミド樹脂 |
JP2000256462A (ja) * | 1998-11-09 | 2000-09-19 | Kanegafuchi Chem Ind Co Ltd | ポリイミド組成物およびその製造方法 |
JP2001042527A (ja) * | 1999-07-29 | 2001-02-16 | Hitachi Chem Co Ltd | 感光性重合体組成物、パターンの製造法及び電子部品 |
JP2001194796A (ja) * | 1999-10-29 | 2001-07-19 | Hitachi Chemical Dupont Microsystems Ltd | ポジ型感光性樹脂組成物、パターンの製造法及び電子部品 |
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- 2007-04-19 WO PCT/JP2007/058551 patent/WO2007125818A1/ja active Search and Examination
- 2007-04-19 JP JP2008513168A patent/JP5141552B2/ja active Active
- 2007-04-19 KR KR1020087026896A patent/KR101281965B1/ko active IP Right Grant
- 2007-04-20 TW TW96114059A patent/TWI432483B/zh active
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JPH03177430A (ja) * | 1989-12-06 | 1991-08-01 | Tomoegawa Paper Co Ltd | ポリアミドイミド樹脂 |
JP2000256462A (ja) * | 1998-11-09 | 2000-09-19 | Kanegafuchi Chem Ind Co Ltd | ポリイミド組成物およびその製造方法 |
JP2001042527A (ja) * | 1999-07-29 | 2001-02-16 | Hitachi Chem Co Ltd | 感光性重合体組成物、パターンの製造法及び電子部品 |
JP2001194796A (ja) * | 1999-10-29 | 2001-07-19 | Hitachi Chemical Dupont Microsystems Ltd | ポジ型感光性樹脂組成物、パターンの製造法及び電子部品 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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USRE43372E1 (en) | 1999-03-05 | 2012-05-08 | Duke University | C16 unsaturated FP-selective prostaglandins analogs |
US8541466B2 (en) | 2000-03-31 | 2013-09-24 | Duke University | Compositions and methods for treating hair loss using non-naturally occurring prostaglandins |
US8618086B2 (en) | 2000-03-31 | 2013-12-31 | Duke University | Compositions and methods for treating hair loss using C16-C20 aromatic tetrahydro prostaglandins |
JP2008033159A (ja) * | 2006-07-31 | 2008-02-14 | Hitachi Chemical Dupont Microsystems Ltd | ネガ型感光性樹脂組成物、パターン硬化膜の製造方法および電子部品 |
JP2008083359A (ja) * | 2006-09-27 | 2008-04-10 | Jsr Corp | 感光性樹脂組成物及び硬化膜 |
US8722739B2 (en) | 2008-10-29 | 2014-05-13 | Novaer Holdings, Inc. | Amino acid salts of prostaglandins |
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TW200806712A (en) | 2008-02-01 |
JP5141552B2 (ja) | 2013-02-13 |
JPWO2007125818A1 (ja) | 2009-09-10 |
TWI432483B (zh) | 2014-04-01 |
KR20090007578A (ko) | 2009-01-19 |
KR101281965B1 (ko) | 2013-07-03 |
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