WO2020070924A1 - 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 - Google Patents
感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品Info
- Publication number
- WO2020070924A1 WO2020070924A1 PCT/JP2019/023925 JP2019023925W WO2020070924A1 WO 2020070924 A1 WO2020070924 A1 WO 2020070924A1 JP 2019023925 W JP2019023925 W JP 2019023925W WO 2020070924 A1 WO2020070924 A1 WO 2020070924A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- group
- component
- resin composition
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 0 Cc1cc(*c2c(*3)cc(C)c(C)c2)c3cc1C Chemical compound Cc1cc(*c2c(*3)cc(C)c(C)c2)c3cc1C 0.000 description 3
- FGDRHQXIHLFUAR-UHFFFAOYSA-N C=CC(OCCC1C2C(C3)C(CCOC(C=C)=O)CC3C2CC1)=O Chemical compound C=CC(OCCC1C2C(C3)C(CCOC(C=C)=O)CC3C2CC1)=O FGDRHQXIHLFUAR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
-
- 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
- C08G73/12—Unsaturated polyimide precursors
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a photosensitive resin composition, a method for producing a cured pattern, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
- a multi-die fan-out wafer-level package (Multi-die Fanout Wafer Level Packaging) is a package that collectively seals a plurality of dies in one package, and has been conventionally proposed. It has attracted a great deal of attention because it can be expected to have lower cost and higher performance than conventional fan-out wafer level packages (where one die is encapsulated in one package).
- An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having excellent resolution and aspect ratio even at a low temperature curing of 200 ° C. or lower, a method for producing a patterned cured product, a cured product, an interlayer insulating film, and a cover coat. It is to provide a layer, a surface protective film and an electronic component.
- the following photosensitive resin composition and the like are provided.
- a photosensitive resin composition containing (C) a photopolymerization initiator, and
- X 1 is a tetravalent group having one or more aromatic groups, and the —COOR 1 group and the —CONH— group are located at ortho positions to each other, and the —COOR 2 group and the —CO Groups are ortho to each other, Y 1 is a divalent group having one or more aromatic groups, R 1 and R 2 are each independently a hydrogen atom, and represented by the following formula (2): Or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R 1 and R 2 is a group represented by the formula (2).)
- R 3 to R 5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.
- R 6 and R 7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4).
- N1 is 0 or 1
- N2 is an integer of 0 to 2
- n1 + n2 is 1 or more.
- At least one of n1 R 6 and n2 R 7 is a group represented by the following formula (4).
- R 9 to R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10.) 7.
- the photosensitive resin composition according to 6, wherein n1 + n2 is 2 or 3. 8. 8.
- the component (D) is 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -p-cresol, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 4- [ethyl (2-hydroxyethyl) amino] -4'-nitroazobenzene, (1E, 6E) -1,7-bis (4-hydroxy-3- Selected from the group consisting of (methoxyphenyl) -1,6-heptadiene-3,5-dione and 1,7-bis (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione
- the photosensitive resin composition according to 1 or more is 1 to
- An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to 18.17.
- a photosensitive resin composition capable of forming a cured product having excellent resolution and aspect ratio even at a low temperature of 200 ° C. or less, a method for producing a patterned cured product, a cured product, an interlayer insulating film, and a cover coat Layers, surface protective films and electronic components can be provided.
- a or B may include either one of A and B, and may include both.
- the term “step” is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. included.
- the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the content of each component in the composition if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity.
- the exemplified materials may be used alone or in combination of two or more unless otherwise specified.
- the “(meth) acryl group” in the present specification means “acryl group” and “methacryl group”.
- the photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as “component (A)”), (B) a polymerizable monomer (hereinafter, “(B) ) Component), (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”), and (D) an ultraviolet absorber (hereinafter also referred to as “component (D) component”).
- component (A) a polyimide precursor having a polymerizable unsaturated bond
- component (B) a polymerizable monomer
- component (C) a photopolymerization initiator
- component (D) component an ultraviolet absorber
- the photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition. Further, the photosensitive resin composition of the present invention is preferably a material for electronic parts.
- the component (A) is not particularly limited, but is preferably a polyimide precursor having a high transmittance when i-line is used as a light source at the time of patterning and exhibiting high cured product properties even at a low temperature of 200 ° C. or lower.
- Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.
- the component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1).
- the content of the structural unit represented by the formula (1) is preferably at least 50 mol%, more preferably at least 80 mol%, and preferably at least 90 mol%, based on all the constituent units of the component (A). More preferred.
- the upper limit is not particularly limited, and may be 100 mol%.
- X 1 is a tetravalent group having one or more aromatic groups
- the —COOR 1 group and the —CONH— group are located at ortho positions to each other
- the —COOR 2 group and the —CO Groups are ortho to each other
- Y 1 is a divalent group having one or more aromatic groups
- R 1 and R 2 are each independently a hydrogen atom, and represented by the following formula (2): Or an aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms, and at least one of R 1 and R 2 is a group represented by the formula (2).
- R 3 to R 5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10 (preferably an integer of 2 to 5) , More preferably 2 or 3).
- the aromatic group may be an aromatic hydrocarbon group, It may be a group heterocyclic group. Aromatic hydrocarbon groups are preferred.
- Examples of the aromatic hydrocarbon group represented by X 1 in the formula (1) include a divalent to tetravalent (divalent, trivalent, or tetravalent) group formed from a benzene ring, and a divalent to tetravalent group formed from naphthalene. And divalent to tetravalent groups formed from perylene.
- Examples of the tetravalent group having one or more aromatic groups represented by X 1 in the formula (1) include, but are not limited to, a tetravalent group represented by the following formula (6).
- X and Y each independently represent a divalent group or a single bond that is not conjugated to a benzene ring to which they are bonded.
- Z is an ether group (—O—) or a sulfide group (—S -) (Preferably -O-).
- the divalent group that is not conjugated to the benzene ring to which each of X and Y is bonded is —O—, —S—, a methylene group, a bis (trifluoromethyl) methylene group, or a difluoromethylene group. And more preferably -O-.
- the aromatic group may be an aromatic hydrocarbon group, It may be a group heterocyclic group. Aromatic hydrocarbon groups are preferred.
- Examples of the aromatic hydrocarbon group represented by Y 1 in the formula (1) include a divalent to tetravalent group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene. And the like.
- Examples of the divalent group having one or more aromatic groups of Y 1 in the formula (1) include a divalent group in which two aromatic groups are bonded via an ether group (—O—). However, it is not limited to this.
- Examples of the divalent group having one or more aromatic groups of Y 1 in the formula (1) include, but are not limited to, a group represented by the following formula (7).
- R 12 to R 19 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.
- Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) represented by R 12 to R 19 in the formula (7) include a methyl group.
- R 12 and R 15 to R 19 may be a hydrogen atom
- R 13 and R 14 may be a monovalent aliphatic hydrocarbon group.
- the monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R 12 to R 19 in the formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, It preferably has 1 to 6 carbon atoms, and examples thereof include a trifluoromethyl group.
- Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms for R 1 and R 2 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n- Butyl group and the like.
- At least one of R 1 and R 2 in the formula (1) is a group represented by the formula (2), and both are preferably groups represented by the formula (2).
- Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms represented by R 3 to R 5 in the formula (2) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. Can be A methyl group is preferred.
- the polyimide precursor having the structural unit represented by the formula (1) is, for example, a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9):
- a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9) By reacting in an organic solvent such as -methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (10), and reacting in an organic solvent to partially introduce an ester group.
- the tetracarboxylic dianhydride represented by the formula (8) and the diamino compound represented by the formula (9) may be used alone or in a combination of two or more.
- X 1 is a group corresponding to X 1 of the formula (1).
- R is a group represented by the above formula (2).
- the component (A) may have a structural unit other than the structural unit represented by the formula (1).
- Examples of the structural unit other than the structural unit represented by Formula (1) include a structural unit represented by Formula (11).
- X 2 is a tetravalent group having one or more aromatic groups
- -COOR 51 group and -CONH- group are at ortho positions to each other
- -COOR 52 group and -COOR Groups are ortho to each other
- Y 2 is a divalent group having one or more aromatic groups
- R 51 and R 52 are each independently a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms. It is a hydrocarbon group.
- Examples of the tetravalent group having one or more aromatic groups of X 2 in the formula (11) include the same as the tetravalent group having one or more aromatic groups of X 1 in the formula (1).
- Examples of the divalent group having one or more aromatic groups represented by Y 2 in the formula (11) include the same divalent groups having one or more aromatic groups represented by Y 1 represented by the formula (1).
- Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R 51 and R 52 in the formula (11) include the same as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms represented by R 1 and R 2 .
- the structural unit other than the structural unit represented by the formula (1) may be used alone or in combination of two or more.
- the content of the structural unit other than the structural unit represented by the formula (1) is preferably less than 50 mol% with respect to all the constituent units of the component (A).
- the ratio of the carboxy group esterified with the group represented by the formula (2) to all carboxy groups and all carboxy esters is preferably 50 mol% or more, and 60 to 100 mol%. Mol% is more preferable, and 70 to 90 mol% is still more preferable.
- the molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of weight average molecular weight.
- the weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.
- the photosensitive resin composition of the present invention contains (B) a polymerizable monomer. Thereby, the heat resistance, mechanical properties, and chemical resistance of the formed cured product can be improved.
- the component (B) is polymerizable with a group (preferably two or more) containing a polymerizable unsaturated double bond (preferably, a photopolymerization initiator) from the viewpoint of improving the crosslink density with the component (A). For this reason, it is preferable to include a polymerizable monomer having a (meth) acryl group).
- the polymerizable monomer preferably has an aliphatic cyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms).
- an aliphatic cyclic skeleton preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms.
- the polymerizable monomer preferably has two or three groups containing a polymerizable unsaturated double bond in order to improve the crosslink density and photosensitivity and to suppress swelling of the pattern after development.
- the component (B) preferably contains a polymerizable monomer represented by the following formula (3).
- R 6 and R 7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4).
- N1 is 0 or 1
- N2 is an integer of 0 to 2
- n1 + n2 is 1 or more (preferably 2 or 3.)
- At least one (preferably 2 or 3) of n1 R 6 and n2 R 7 is It is a group represented by the formula (4).
- the two R 7 may be the same or different.
- R 9 to R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10 (preferably 0, 1 or 2 ).)
- the component (B) contains a polymerizable monomer represented by the following formula (5).
- component (B) for example, the following polymerizable monomers may be used.
- R 21 to R 24 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (4).
- n3 is an integer of 1 to 3 (preferably 2 or 3).
- n4 is an integer of 1 to 3 (preferably 2 or 3).
- n5 is 0 or 1
- n6 is 0 or 1.
- n5 + n6 is 1 or more (preferably 2).
- two or more R 21 When two or more R 21 are present, two or more R 21 may be the same or different. When two or more R 22 are present, two or more R 22 may be the same or different.
- At least one (preferably 2 or 3) of the n3 R 21 is a group represented by the above formula (4).
- At least one (preferably 2 or 3) of the n4 R 22 is a group represented by the above formula (4).
- n5 or at least one of R 23 and n6 amino R 24 (preferably 2) is a group represented by the above formula (4).
- Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R 6 and R 7 in the formula (3) and R 21 to R 24 in the formula (12) include a carbon atom having 1 carbon atom represented by R 1 and R 2 in the formula (1). And the same as the aliphatic hydrocarbon groups (1) to (4).
- the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R 9 to R 11 in the formula (4) is the same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R 3 to R 5 in the formula (2). Things.
- a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton may be used.
- the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, , 4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and the like.
- tetraethylene glycol dimethacrylate pentaerythritol tetraacrylate, and methanetetrayltetrakis tetrakisacrylate (methyleneoxyethylene) are preferred.
- the component (B) may be used alone or in combination of two or more.
- the content of the component (B) is preferably 1 to 50 parts by mass based on 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 3 to 50 parts by mass, and still more preferably 5 to 40 parts by mass. When it is within the above range, a practical relief pattern is easily obtained, and the post-development residue of the unexposed portion is easily suppressed.
- benzophenone derivatives such as benzophenone, methyl 2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone; Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone; Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxyethyl acetal, Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl
- oxime esters are preferred in terms of photosensitivity.
- the component (C) includes (C1) one or more compounds selected from the group consisting of a compound represented by the following formula (15-1) and a compound represented by the following formula (15-2) (hereinafter, “( C1) component).
- the component (C1) preferably has a higher sensitivity to actinic rays than the component (C2) described below, and is preferably a highly sensitive photosensitizer.
- R 11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5.
- R 12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
- R 13A and R 14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 (preferably 1 to 4) carbon atoms, a phenyl group or a tolyl group.
- R 11A may be the same or different.
- R 11A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1.
- R 12A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group.
- R 13A and R 14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- the compound represented by the formula (15-1) includes, for example, a compound represented by the following formula (15A), and is available as “IRGACURE OXE 02” manufactured by BASF Japan Ltd.
- R 15A represents —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH
- R 16A and R 17A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group. It is.
- b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R 15 may be the same or different.
- R 15A is preferably -O (CH 2 ) 2 OH.
- b1 is preferably 0 or 1.
- R 16A is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group.
- R 17A is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.
- Examples of the compound represented by the formula (15-2) include a compound represented by the following formula (15B), which is available as “NCI-930” manufactured by ADEKA Corporation.
- the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as “(C2) component”).
- the component (C2) preferably has lower sensitivity to actinic rays than the component (C1), and is preferably a photosensitive agent having a standard sensitivity.
- R 21A is an alkyl group having 1 to 12 carbon atoms
- R 22A and R 23A are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms).
- c1 is an integer of 2 or more, R 21A may be the same or different.
- R 22A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- R 23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, even more preferably a methoxy group or an ethoxy group.
- Examples of the compound represented by the formula (16) include a compound represented by the following formula (16A), which is available as “G-1820 (PDO)” manufactured by Lambson.
- the component (C) may be used alone or in combination of two or more.
- the component (C) preferably contains at least one selected from the group consisting of the component (C1) and the component (C2). Further, the component (C) preferably contains the component (C1) and the component (C2) from the viewpoint of adjusting the transmittance.
- the content of the component (C) is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 15 parts by mass, and still more preferably from 0.1 to 20 parts by mass, per 100 parts by mass of the component (A). 10 parts by mass. When it is in the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.
- the content of the component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of the component (A).
- the amount is 5 parts by mass, more preferably 0.2 to 2.0 parts by mass.
- the content of the component (C2) is usually 0.5 to 15.0 parts by mass, preferably 1.0 to 10% by mass, per 100 parts by mass of the component (A). 0 parts by mass.
- the content of the component (C1) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the component (A), and the component (C2) Is preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the component (A).
- the mass ratio of the content of the component (C1) to the content of the component (C2) is preferably from 1: 3 to 1:70, and more preferably from 1: 5 to 1:70. 1:50.
- the photosensitive resin composition of the present invention contains (D) an ultraviolet absorber. This can suppress crosslinking of the unexposed portion due to irregular reflection upon irradiation with actinic rays.
- the component (D) at a concentration of 10 mg / L preferably has an absorbance at 365 nm of 0.05 or more, more preferably 0.1 or more.
- component (D) for example, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3 , 5-Di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalic Imidylmethyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzoto 2-yl) -4,6-bis (1-methyl-1-phenylethyl
- benzotriazole compound a benzophenone compound, an azobenzene compound, or a polyphenol compound.
- the component (D) may be used alone or in combination of two or more.
- the content of the component (D) is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the component (A), from the viewpoint of excellent resolution (resolution). 0.2 parts by mass or more is more preferable.
- the content of the component (D) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less based on 100 parts by mass of the component (A).
- the photosensitive resin composition of the present invention may further contain (E) a polymerization inhibitor (hereinafter, also referred to as “component (E)”) from the viewpoint of ensuring storage stability.
- component (E) include a radical polymerization inhibitor and a radical polymerization inhibitor.
- component (E) examples include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2.
- -Naphthylamine cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, and 1,4,4-trimethyl-2,3-diazabicyclo [3.2.2] -non-2-ene- And the like. 2,3-dixoid) and the like.
- the component (E) may be used alone or in combination of two or more.
- the content of the component (E) is preferably from 100 parts by mass of the component (A) from the viewpoints of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product. , 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass.
- the photosensitive resin composition of the present invention may further contain (F) a rust inhibitor (hereinafter, also referred to as “component (F)”) from the viewpoint of suppressing corrosion of copper and copper alloy and preventing discoloration. Good.
- component (F) for example, 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole , 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4 -Triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1 , 2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino
- the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A). -4 parts by mass is more preferred.
- the photosensitive resin composition of the present invention further comprises (G) a silane coupling agent (adhesion aid) (hereinafter referred to as “(G) component”) from the viewpoint of improving the adhesion of the obtained cured film to the substrate. ) May be included.
- a silane coupling agent adheresion aid
- the component (G) reacts with the component (A) in the heat treatment after development to form a crosslink, or the component (G) itself polymerizes in the heat treatment step. Thereby, the adhesiveness between the obtained cured product and the substrate can be further improved.
- Examples of the component (G) include compounds having a urea bond (—NH—CO—NH—). Thereby, even when the curing is performed at a low temperature of 200 ° C. or less, the adhesiveness to the substrate can be further improved.
- the compound represented by the following formula (13) is more preferable in that it exhibits excellent adhesion when cured at a low temperature.
- R 31 and R 32 are each independently an alkyl group having 1 to 5 carbon atoms. A is an integer of 1 to 10, and b is an integer of 1 to 3.
- Specific examples of the compound represented by the formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. And 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, with 3-ureidopropyltriethoxysilane being preferred.
- a silane coupling agent having a hydroxy group or a glycidyl group may be used as the component (G).
- a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in a molecule are used in combination, it is possible to further improve the adhesion of a cured product to a substrate during low-temperature curing.
- silane coupling agent having a hydroxy group or a glycidyl group examples include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and tert-silane.
- R 33 is a monovalent organic group having a hydroxy group or a glycidyl group
- R 34 and R 35 are each independently an alkyl group having 1 to 5 carbon atoms.
- An integer of 10 and d is an integer of 1 to 3.
- Examples of the compound represented by the formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutylto Silane and the like.
- Commercially available products include “KBM403” (trade name
- the silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and more preferably a silane coupling agent having an amino group or an amide bond.
- the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidyl) (Xymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane and the like.
- Examples of the silane coupling agent having an amide bond include compounds represented by the following formula.
- R 36 is a hydroxy group or a glycidyl group, e and f are each independently an integer of 1 to 3
- R 37 is a methyl group, an ethyl group or a propyl group.
- triethoxysilylpropylethyl carbamate may be used as the component (G).
- component (G) one type may be used alone, or two or more types may be used in combination.
- the content of the component (G) is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A). Parts by mass are more preferred.
- the photosensitive resin composition of the present invention further comprises (H) a sensitizer (hereinafter, referred to as “(H) component”) from the viewpoint of maintaining both the residual film ratio in a wide range of exposure dose and good resolution. ) May be included.
- (H) component a sensitizer
- the component (H) includes Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, Anthraquinone, methylanthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldi Sul
- component (H) one type may be used alone, or two or more types may be used in combination.
- the amount of the component (H) is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of the component (A). Is more preferred.
- the photosensitive resin composition of the present invention may further contain (I) a thermal polymerization initiator (hereinafter, also referred to as “component (I)”) from the viewpoint of accelerating the polymerization reaction.
- component (I) is not decomposed by heating (drying) for removing a solvent during film formation, but is decomposed by heating during curing to generate radicals.
- Compounds that promote the polymerization reaction of component (B) are preferred.
- the component (I) is preferably a compound having a decomposition point of 110 ° C to 200 ° C, and more preferably a compound having a decomposition point of 110 ° C to 175 ° C from the viewpoint of accelerating the polymerization reaction at a lower temperature.
- ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, Peroxy ketals such as 1-di (t-butylperoxy) cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, dicumyl peroxide Dialkyl peroxides such as -t-butyl peroxide and the like, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbon
- one type may be used alone, or two or more types may be used in combination.
- the content of the component (I) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to ensure good flux resistance.
- the content is more preferably from 2 to 20 parts by mass, and even more preferably from 0.3 to 10 parts by mass from the viewpoint of suppressing the decrease in solubility due to decomposition during drying.
- the photosensitive resin composition of the present invention may further contain a solvent (J) (hereinafter, also referred to as “component (J)”).
- component (J) N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethyl morpholine and the like.
- N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylformamide are preferred from the viewpoint of excellent solubility of each component and coatability in forming a photosensitive resin film.
- N, N-Dimethylacetamide is preferably used.
- component (J) a compound represented by the following formula (21) may be used.
- R 41 to R 43 are each independently an alkyl group having 1 to 10 carbon atoms.
- examples of the alkyl group having 1 to 10 (preferably 1 to 3, more preferably 1 or 3) carbon atoms of R 41 to R 43 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like.
- the compound represented by the formula (21) is preferably 3-methoxy-N, N-dimethylpropanamide (for example, trade name “KJCMPA-100” (manufactured by KJ Chemicals Corporation)).
- the component (J) one type may be used alone, or two or more types may be used in combination.
- the content of the component (J) is not particularly limited, but is generally 50 to 1000 parts by mass based on 100 parts by mass of the component (A).
- the photosensitive resin composition of the present invention may further contain a surfactant or a leveling agent.
- surfactant or the leveling agent examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and the like. , “F173", “R-08” (above, manufactured by DIC Corporation), trade names “Florado FC430", “FC431” (above, manufactured by Sumitomo 3M Limited), trade name “Organosiloxane Polymer KP341" (Shin-Etsu) Chemical Industry Co., Ltd.).
- the surfactant and the leveling agent may be used alone or in a combination of two or more.
- the content of the surfactant or the leveling agent is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, per 100 parts by mass of the component (A).
- the amount is 0.05 to 3 parts by mass.
- the photosensitive resin composition of the present invention essentially comprises the components (A) to (D), and optionally the components (E) to (I), a surfactant, and a leveling agent. And may contain other unavoidable impurities as long as the effects of the present invention are not impaired. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the photosensitive resin composition of the present invention, except for the component (J), (A) to (D) components, It may be composed of components (A) to (I), or components (A) to (D), and optionally components (E) to (I), a surfactant, and a leveling agent.
- the cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
- the cured product of the present invention may be used as a pattern cured product or a cured product without a pattern.
- the thickness of the cured product of the present invention is preferably 5 to 20 ⁇ m.
- the cured product of the present invention preferably has a pattern having an aspect ratio of 1 or more, more preferably has a pattern of 1.2 or more, and particularly preferably has a pattern of 1.5 or more.
- the aspect ratio can be calculated, for example, by taking a cross section of a cured pattern using a scanning electron microscope (SEM), measuring the film thickness and the opening width from the image, and using the following formula.
- SEM scanning electron microscope
- a step of applying the above-described photosensitive resin composition on a substrate and drying to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form a resin film includes a step of obtaining, a step of developing the resin film after pattern exposure using an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thereby, a cured pattern can be obtained.
- a method for producing a cured product having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of performing heat treatment. Further, a step of exposing may be provided.
- the substrate examples include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), a metal oxide insulator substrate such as a TiO 2 substrate and a SiO 2 substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.
- a semiconductor substrate such as a Si substrate (silicon wafer)
- a metal oxide insulator substrate such as a TiO 2 substrate and a SiO 2 substrate
- silicon nitride substrate silicon nitride substrate
- copper substrate examples include a copper alloy substrate.
- the coating method is not particularly limited, but can be performed using a spinner or the like.
- Drying can be performed using a hot plate, an oven, or the like.
- the drying temperature is preferably from 90 to 150 ° C., and more preferably from 90 to 120 ° C. from the viewpoint of ensuring the dissolution contrast.
- the drying time is preferably 30 seconds to 5 minutes. Drying may be performed two or more times. Thereby, a photosensitive resin film in which the above-described photosensitive resin composition is formed in a film shape can be obtained.
- the thickness of the photosensitive resin film is preferably 5 to 100 ⁇ m, more preferably 6 to 50 ⁇ m, and still more preferably 7 to 30 ⁇ m.
- a predetermined pattern is exposed through a photomask.
- the actinic rays to be radiated include ultraviolet rays such as i-rays, visible rays, and radiation, but are preferably i-rays.
- a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, or the like can be used as the exposure device.
- post-exposure bake may be performed if necessary.
- the post-exposure baking temperature is preferably from 60 ° C. to 160 ° C.
- the post-exposure baking time is preferably from 0.5 minutes to 5 minutes.
- a patterned resin film (patterned resin film) can be obtained.
- a negative photosensitive resin composition when used, unexposed portions are removed with a developer.
- the organic solvent used as the developer a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
- the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
- the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.
- a surfactant may be added to the developer.
- the addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer.
- the development time can be, for example, twice as long as the time until the photosensitive resin film is immersed and completely dissolved.
- the development time varies depending on the component (A) used, it is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.
- washing may be performed with a rinsing solution.
- a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like may be used alone or in a suitable mixture, or may be used in a stepwise combination. Good.
- the polyimide precursor of the component (A) undergoes a dehydration and ring closure reaction by the heat treatment step, and usually becomes a corresponding polyimide.
- the temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and further preferably 200 ° C. or lower or 160 to 200 ° C. By being within the above range, damage to the substrate and the device can be suppressed small, the device can be produced with high yield, and energy saving in the process can be realized.
- the time of the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the content is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can sufficiently proceed.
- the atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but is preferably under a nitrogen atmosphere from the viewpoint of preventing oxidation of the pattern resin film.
- Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.
- the cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
- a highly reliable semiconductor device, multilayer wiring board, various electronic devices, laminated Electronic components such as devices (such as a multi-die fan-out wafer level package) can be manufactured.
- FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present invention.
- a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. It is formed. After that, an interlayer insulating film 4 is formed on the semiconductor substrate 1.
- a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4, and a window 6A is formed by a known photolithography technique so that a predetermined portion of the interlayer insulating film 4 is exposed.
- the interlayer insulating film 4 with the window 6A exposed is selectively etched to provide a window 6B.
- the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.
- the second conductor layer 7 is formed by using a known photolithography technique, and is electrically connected to the first conductor layer 3.
- each layer can be formed by repeating the above steps.
- a window 6C is opened by pattern exposure using the above-mentioned photosensitive resin composition, and a surface protective film 8 is formed.
- the surface protection film 8 protects the second conductor layer 7 from external stress, ⁇ -rays and the like, and the obtained semiconductor device has excellent reliability.
- the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.
- UV absorber D1 Adekastab LA-29 (manufactured by ADEKA Corporation, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol)
- D2 ADK STAB LA-24 (2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, manufactured by ADEKA Corporation)
- D3 ADK STAB LA-32 (2- (2H-benzotriazol-2-yl) -p-cresol, manufactured by ADEKA Corporation)
- D4 SEESORB106 (Cipro Kasei Co., Ltd., 2,2 ', 4,4'-tetrahydroxybenzophenone)
- D5 SEESORB107 (2,2'-dihydroxy-4,4'-dimethoxybenzophenone, manufactured by Cipro Kasei Co., Ltd.)
- D6 Disperse Red 1 (manufactured by Hitachi
- sensitizer H1 EMK (manufactured by Aldrich, 4,4'-bis (diethylamino) benzophenone)
- the absorbance of D1 to D8 was measured under the following conditions. Table 1 shows the results. D1 to D8 were each dissolved in chloroform and adjusted to 10 mg / L to prepare a measurement sample. Measuring equipment: U-3900H (manufactured by Hitachi High-Tech Science Corporation) Measurement conditions: cell length: 10.0 mm
- Synthesis Example 1 (Synthesis of A1) 47.1 g (152 mmol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (ODPA), 5.54 g (43 mmol) of 2-hydroxyethyl methacrylate (HEMA) and a catalytic amount of 1,4- Diazabicyclo [2.2.2.
- Octanetriethylenediamine is dissolved in 380 g of N-methyl-2-pyrrolidone (NMP), stirred at 45 ° C.
- the reaction solution was dropped into distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
- the weight average molecular weight was determined by gel permeation chromatography (GPC) using standard polystyrene conversion under the following conditions.
- the weight average molecular weight of A1 was 35,000.
- THF tetrahydrofuran
- DMF dimethylformamide
- esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions.
- the esterification rate was 81 mol% with respect to all carboxy groups (to all carboxy groups and all carboxy esters) of the polyamic acid (the remaining 19 mol% was carboxy groups).
- Synthesis Example 2 (Synthesis of A2) 47.1 g (152 mmol) of ODPA and 2.77 g (21 mmol) of HEMA and a catalytic amount of 1,4-diazabicyclo [2.2.2. ] Octanetriethylenediamine was dissolved in 500 g of NMP, stirred at 45 ° C for 1 hour, cooled to 25 ° C, and 30.0 g (141 mmol) of 2,2'-dimethylbenzidine and 145 mL of dried NMP were added. After stirring at 150 ° C. for 150 minutes, the mixture was cooled to room temperature.
- esterification ratio of A2 was calculated by performing NMR measurement under the same conditions as in Synthesis Example 1.
- the esterification rate was 73 mol% based on the total carboxy groups of the polyamic acid (based on the total carboxy groups and all carboxy esters) (the remaining 27 mol% was carboxy groups).
- Synthesis Example 3 (Synthesis of A3) 62.0 g (200 mmol) of ODPA, 5.2 g (40.0 mmol) of HEMA, and a catalytic amount of 1,4-diazabicyclo [2.2.2] octanetriethylenediamine were dissolved in 250 g of NMP, and stirred at 45 ° C. for 1 hour. After cooling to °C, 5.5 g (50.9 mmol) of m-phenylenediamine, 23.8 g (119 mmol) of oxydianiline (4,4′-diaminodiphenyl ether) and 100 mL of dried NMP were added, followed by stirring at 45 ° C. for 150 minutes.
- Synthesis Example 4 (Synthesis of A4) 43.6 g (200 mmol) of pyromellitic dianhydride (PMDA), 54.9 g (401 mmol) of HEMA and 0.220 g of hydroquinone were dissolved in 394 g of NMP, and 1,8-diazabicycloundecene was added thereto in a catalytic amount. After stirring at 24 ° C. for 24 hours, esterification was performed to obtain a pyromellitic acid-hydroxyethyl methacrylate diester solution. This solution is referred to as a PMDA-HEMA solution.
- PMDA-HEMA solution 43.6 g (200 mmol) of pyromellitic dianhydride (PMDA), 54.9 g (401 mmol) of HEMA and 0.220 g of hydroquinone was dissolved in 394 g of NMP, and 1,8-diazabicycloundecene was added thereto in a catalytic amount.
- esterification ratio of A4 was calculated by performing NMR measurement under the same conditions as in Synthesis Example 1.
- the esterification ratio was 97 mol% with respect to all carboxy groups (to all carboxy groups and all carboxy esters) of the polyamic acid (the remaining 3 mol% was carboxy groups).
- Examples 1 to 24 and Comparative Examples 1 to 7 [Preparation of photosensitive resin composition]
- the photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were prepared using the components and amounts shown in Tables 2 and 3.
- the compounding amounts in Tables 2 and 3 are parts by mass of each component with respect to 100 parts by mass of the component (A).
- the obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a dried film.
- a photosensitive resin film having a thickness of 7 to 10 ⁇ m was formed.
- the development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
- a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was exposed at an exposure amount shown in Tables 2 and 3 using an i-line stepper FPA-3000iW (manufactured by Canon Inc.).
- Examples 5a, 6a, 10a, 20a to 23a and Comparative Examples 1a to 4a, 7a, 8a [Preparation of photosensitive resin composition]
- the photosensitive resin compositions of Examples 5a, 6a, 10a, 20a to 23a and Comparative Examples 1a to 4a, 7a, 8a were prepared using the components and the amounts shown in Table 4.
- the compounding amounts in Table 4 are parts by mass of each component with respect to 100 parts by mass of the component (A).
- a photosensitive resin film was formed in the same manner as in Examples 1 to 24 and Comparative Examples 1 to 7.
- the development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
- a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was applied to a photomask for forming a via having a diameter of 1 ⁇ m to 100 ⁇ m using FPA-3000iW at an exposure amount shown in Table 4. Irradiation and exposure were performed.
- the exposed resin film was paddle-developed with Cyclopentanone using Act8 for the above development time, and then rinsed with PGMEA to obtain a patterned resin film.
- Examples 25 to 27 and Comparative Examples 8 to 10 [Preparation of photosensitive resin composition]
- the photosensitive resin compositions of Examples 25 to 27 and Comparative Examples 8 to 10 were prepared using the components and amounts shown in Table 5.
- the blending amounts in Table 5 are parts by mass of each component with respect to 100 parts by mass of the component (A).
- the obtained photosensitive resin composition is spin-coated on a silicon wafer using Act8, dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a photosensitive resin having a dry film thickness of 12 to 15 ⁇ m.
- a film was formed.
- the development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
- a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was applied to a photomask for forming a via having a diameter of 1 ⁇ m to 100 ⁇ m using FPA-3000iW at an exposure amount shown in Table 5. Irradiation and exposure were performed.
- the exposed resin film was paddle-developed with Cyclopentanone using Act8 for the above development time, and then rinsed with PGMEA to obtain a patterned resin film.
- Examples 28 and 29 and Comparative Examples 11 and 12 [Preparation of photosensitive resin composition]
- the photosensitive resin compositions of Examples 28 and 29 and Comparative Examples 11 and 12 were prepared using the components and amounts shown in Table 6.
- the blending amounts in Table 6 are parts by mass of each component with respect to 100 parts by mass of the component (A).
- the obtained photosensitive resin composition is spin-coated on a silicon wafer using Act8, dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a photosensitive resin having a dry film thickness of 12 to 15 ⁇ m. A film was formed. The development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone. Further, a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was applied to a photomask for forming a via having a diameter of 1 ⁇ m to 100 ⁇ m using FPA-3000iW at an exposure amount shown in Table 6. Irradiation and exposure were performed.
- the photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, a surface protective film, and the like, and the interlayer insulating film, the cover coat layer, or the surface protective film of the present invention can be used for electronic components and the like. Can be.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
1.(A)重合性の不飽和結合を有するポリイミド前駆体、
(B)重合性モノマー、
(C)光重合開始剤、及び
(D)紫外線吸収剤を含有する感光性樹脂組成物。
2.前記(A)成分が、下記式(1)で表される構造単位を有するポリイミド前駆体である1に記載の感光性樹脂組成物。
3.前記(B)成分が、重合性の不飽和二重結合を含む基を有する重合性モノマーを含む1又は2に記載の感光性樹脂組成物。
4.前記重合性の不飽和二重結合を含む基が、2以上である3に記載の感光性樹脂組成物。
5.前記重合性モノマーが、脂肪族環状骨格を有する1~4のいずれかに記載の感光性樹脂組成物。
6.前記(B)成分が、下記式(3)で表される重合性モノマーを含む1~3のいずれかに記載の感光性樹脂組成物。
7.n1+n2が、2又は3である6に記載の感光性樹脂組成物。
8.前記(B)成分が、下記式(5)で表される重合性モノマーを含む1~7のいずれかに記載の感光性樹脂組成物。
10.前記(D)成分が、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、アゾベンゼン系化合物、及びポリフェノール系化合物からなる群から選択される1以上である1~9に記載の感光性樹脂組成物。
11.前記(D)成分が、2-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-p-クレゾール、2,2′,4,4′-テトラヒドロキシベンゾフェノン、2,2′-ジヒドロキシ-4,4′-ジメトキシベンゾフェノン、4-[エチル(2-ヒドロキシエチル)アミノ]-4′-ニトロアゾベンゼン、(1E,6E)-1,7-ビス(4-ヒドロキシ-3-メトキシフェニル)-1,6-ヘプタジエン-3,5-ジオン、及び1,7-ビス(4-ヒドロキシフェニル)-1,6-ヘプタジエン-3,5-ジオンからなる群から選択される1以上である1~10に記載の感光性樹脂組成物。
12.さらに、(I)熱重合開始剤を含む1~11のいずれかに記載の感光性樹脂組成物。
13.1~12のいずれかに記載の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて、現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、を含むパターン硬化物の製造方法。
14.前記加熱処理の温度が200℃以下である13に記載のパターン硬化物の製造方法。
15.1~12のいずれかに記載の感光性樹脂組成物を硬化した硬化物。
16.パターン硬化物である15に記載の硬化物。
17.15又は16に記載の硬化物を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
18.17に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。
「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。また、本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。さらに、例示材料は特に断らない限り単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本明細書における「(メタ)アクリル基」とは、「アクリル基」及び「メタクリル基」を意味する。
また、本発明の感光性樹脂組成物は、電子部品用材料であることが好ましい。
式(1)で表される構造単位の含有量は、(A)成分の全構成単位に対して、50モル%以上であることが好ましく、80モル%以上がより好ましく、90モル%以上がさらに好ましい。上限は特に限定されず、100モル%でもよい。
式(8)で表されるテトラカルボン酸二無水物及び式(9)で表されるジアミノ化合物は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
式(1)で表される構造単位以外の構造単位としては、式(11)で表される構造単位等が挙げられる。
式(11)のY2の1以上の芳香族基を有する2価の基は、式(1)のY1の1以上の芳香族基を有する2価の基と同様のものが挙げられる。
式(11)のR51及びR52の炭素数1~4の脂肪族炭化水素基は、R1及びR2の炭素数1~4の脂肪族炭化水素基と同様のものが挙げられる。
重量平均分子量は、例えばゲルパーミエーションクロマトグラフィー法によって測定することができ、標準ポリスチレン検量線を用いて換算することによって求めることができる。
R22が2以上存在する場合、2以上のR22は同一でもよく、異なっていてもよい。
n4個のR22の少なくとも1つ(好ましくは2又は3)は、上記式(4)で表される基である。
n5個のR23及びn6個のR24の少なくとも1つ(好ましくは2)は、上記式(4)で表される基である。
また、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、
テトラメチロールメタンテトラアクリレート、テトラメチロールメタンテトラメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、テトラキスアクリル酸メタンテトライルテトラキス(メチレンオキシエチレン)、エトキシ化イソシアヌル酸トリアクリレート、エトキシ化イソシアヌル酸トリメタクリレート、アクリロイルオキシエチルイソシアヌレート、メタクリロイルオキシエチルイソシアヌレート等が挙げられる。
上記範囲内である場合、実用的なレリーフパターンが得られやすく、未露光部の現像後残滓を抑制しやすい。
2,2′-ジエトキシアセトフェノン、2-ヒドロキシ-2-メチルプロピオフェノン、1-ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体、
チオキサントン、2-メチルチオキサントン、2-イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体、
ベンジル、ベンジルジメチルケタール、ベンジル-β-メトキシエチルアセタール等のベンジル誘導体、
ベンゾイン、ベンゾインメチルエーテル等のベンゾイン誘導体、及び
1-フェニル-1,2-ブタンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-メトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-1,2-プロパンジオン-2-(O-ベンゾイル)オキシム、1,3-ジフェニルプロパントリオン-2-(O-エトキシカルボニル)オキシム、1-フェニル-3-エトキシプロパントリオン-2-(O-ベンゾイル)オキシム、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)、下記式で表される化合物等のオキシムエステル類などが好ましく挙げられるが、これらに限定されるものではない。
(C1)成分は、活性光線に対する感度が後述する(C2)成分より高いことが好ましく、高感度な感光剤であることが好ましい。
R15Aは、好ましくは-O(CH2)2OHである。b1は好ましくは0又は1である。R16Aは、好ましくは炭素数1~6のアルキル基であり、より好ましくはメチル基又はヘキシル基である。R17Aは、好ましくは炭素数1~6のアルキル基又はフェニル基であり、より好ましくはメチル基又はフェニル基である。
(C2)成分は、活性光線に対する感度が(C1)成分より低いことが好ましく、標準的な感度の感光剤であることが好ましい。
また、(C)成分は、透過率の調整の観点から、(C1)成分及び(C2)成分を含むことが好ましい。
上記範囲内の場合、光架橋が膜厚方向で均一となりやすく、実用的なレリーフパターンを得やすくなる。
これにより、活性光線照射の際に乱反射による未露光部の架橋を抑制できる。(D)成分は、10mg/Lの濃度で、365nmにおける吸光度が0.05以上であることが好ましく、0.1以上であることがより好ましい。
2-(2-ヒドロキシ-5-メチルフェニル)-2H-ベンゾトリアゾール、2-(3-tert-ブチル-2-ヒドロキシ-5-メチルフェニル)-5-クロロ-2H-ベンゾトリアゾール、2-(3,5-ジ-tert-ペンチル-2-ヒドロキシフェニル)-2H-ベンゾトリアゾール、2-(2H-ベンゾトリアゾール-2-イル)-4-メチル-6-(3,4,5,6-テトラヒドロフタルイミジルメチル)フェノール、2-(2-ヒドロキシ-4-オクチルオキシフェニル)-2H-ベンゾトリアゾール、2-(2-ヒドロキシ-5-tert-オクチルフェニル)-2H-ベンゾトリアゾール、2-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-p-クレゾール)等のベンゾトリアゾール系化合物、
フェニルサリチレート、4-tert-ブチルフェニルサリチレート等のサリチル酸エステル系化合物、
2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-n-オクチルオキシベンゾフェノン、4-n-ドデシルオキシ-2-ヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン-5-スルホン酸三水和物、2,2′,4,4′-テトラヒドロキシベンゾフェノン、2,2′-ジヒドロキシ-4,4′-ジメトキシベンゾフェノン等のベンゾフェノン系化合物、
2-シアノ-3,3-ジフェニルアクリル酸エチル等のジフェニルアクリレート系化合物、
シアノアクリレート系化合物、
2-シアノ-3,3-ジフェニルアクリル酸(2′-エチルヘキシル)等のジフェニルシアノアクリレート系化合物、
ベンゾチアゾール系化合物、
4-[エチル(2-ヒドロキシエチル)アミノ]-4′-ニトロアゾベンゼン等のアゾベンゼン系化合物、
ピロガロール、フロログリシン、カテキン、エピカテキン、ガロカテキン、カテキンガレート、ガロカテキンガレート、エピカテキンガレート、エピガロカテキンガレート、エピガロカテキン、ルチン、クエルセチン、クエルセタギン、クエルセタゲチン、ゴシペチン、ペラルゴニジン、シアニジン、オーランチニジン、ルテオリニジン、ペオニジン、ロシニジン、(1E,6E)-1,7-ビス(4-ヒドロキシ-3-メトキシフェニル)-1,6-ヘプタジエン-3,5-ジオン、1,7-ビス(4-ヒドロキシフェニル)-1,6-ヘプタジエン-3,5-ジオン等のポリフェノール系化合物、
[2,2′-チオビス(4-tert-オクチルフェノレート)]-2-エチルヘキシルアミンニッケル(II)等のニッケル錯塩系化合物などが挙げられる。
(D)成分の含有量は、(A)成分100質量部に対して、5質量部以下が好ましく、3質量部以下がより好ましく、2質量部以下がさらに好ましい。これにより、活性光線照射の際に組成物の表面での吸収が増大して内部の光硬化が不充分となることを抑えることができる。
(E)成分としては、ラジカル重合禁止剤、ラジカル重合抑制剤等が挙げられる。
(F)成分としては、例えば、1,2,4-トリアゾール、1,2,3-トリアゾール、1,2,5-トリアゾール、3-メルカプト-4-メチル-4H-1,2,4-トリアゾール、3-メルカプト-1,2,4-トリアゾール、4-アミノ-3,5-ジメチル-4H-1,2,4-トリアゾール、4-アミノ-3,5-ジプロピル-4H-1,2,4-トリアゾール、3-アミノ-5-イソプロピル-1,2,4-トリアゾール、4-アミノ-3-メルカプト-5-メチル-4H-1,2,4-トリアゾール、3-アミノ-5-メルカプト-1,2,4-トリアゾール、3-アミノ-5-メチル-4H-1,2,4-トリアゾール、4-アミノ-1,2,4-トリアゾール、4-アミノ-3,5-ジメチル-1,2,4-トリアゾール、4-アミノ-5-メチル-4H-1,2,4-トリアゾール-3-チオール、3,5-ジアミノ-1H-1,2,4-トリアゾール、5-メチル-1H-ベンゾトリアゾール、5,6-ジメチルベンゾトリアゾール、5-アミノ-1H-ベンゾトリアゾール、ベンゾトリアゾール-4-スルホン酸、1,2,3-ベンゾトリアゾール等のトリアゾール誘導体、及び1H-テトラゾール、5-メチル-1H-テトラゾール、5-(メチルチオ)-1H-テトラゾール、5-(エチルチオ)-1H-テトラゾール、5-フェニル-1H-テトラゾール、5-ニトロ-1H-テトラゾール1-メチル-1H-テトラゾール、5,5’-ビス-1H-テトラゾール、5-アミノ-1H-テトラゾール等のテトラゾール誘導体などが挙げられる。
(F)成分は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
低温での硬化を行った際の接着性の発現に優れる点で、下記式(13)で表される化合物がより好ましい。
ヒドロキシ基又はグリシジル基を有するシランカップリング剤としては、メチルフェニルシランジオール、エチルフェニルシランジオール、n-プロピルフェニルシランジオール、イソプロピルフェニルシランジオール、n-ブチルフェニルシランジオール、イソブチルフェニルシランジオール、tert-ブチルフェニルシランジオール、ジフェニルシランジオール、エチルメチルフェニルシラノール、n-プロピルメチルフェニルシラノール、イソプロピルメチルフェニルシラノール、n-ブチルメチルフェニルシラノール、イソブチルメチルフェニルシラノール、tert-ブチルメチルフェニルシラノール、エチルn-プロピルフェニルシラノール、エチルイソプロピルフェニルシラノール、n-ブチルエチルフェニルシラノール、イソブチルエチルフェニルシラノール、tert-ブチルエチルフェニルシラノール、メチルジフェニルシラノール、エチルジフェニルシラノール、n-プロピルジフェニルシラノール、イソプロピルジフェニルシラノール、n-ブチルジフェニルシラノール、イソブチルジフェニルシラノール、tert-ブチルジフェニルシラノール、フェニルシラントリオール、1,4-ビス(トリヒドロキシシリル)ベンゼン、1,4-ビス(メチルジヒドロキシシリル)ベンゼン、1,4-ビス(エチルジヒドロキシシリル)ベンゼン、1,4-ビス(プロピルジヒドロキシシリル)ベンゼン、1,4-ビス(ブチルジヒドロキシシリル)ベンゼン、1,4-ビス(ジメチルヒドロキシシリル)ベンゼン、1,4-ビス(ジエチルヒドロキシシリル)ベンゼン、1,4-ビス(ジプロピルヒドロキシシリル)ベンゼン、1,4-ビス(ジブチルヒドロキシシリル)ベンゼン、及び下記式(14)で表わされる化合物等が挙げられる。中でも、特に、基板との接着性をより向上させるため、式(14)で表される化合物が好ましい。
市販品としては、商品名「KBM403」(信越化学工業株式会社製)等が挙げられる。
さらにアミノ基を有するシランカップリング剤としては、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリエトキシシラン、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリメトキシシラン、ビス(2-グリシドキシメチル)-3-アミノプロピルトリエトキシシラン、ビス(2-ヒドロキシメチル)-3-アミノプロピルトリメトキシシラン等が挙げられる。
R36-(CH2)e-CO-NH-(CH2)f-Si(OR37)3
(R36はヒドロキシ基又はグリシジル基であり、e及びfは、それぞれ独立に、1~3の整数であり、R37はメチル基、エチル基又はプロピル基である)
(I)成分としては、成膜時に溶剤を除去するための加熱(乾燥)では分解せず、硬化時の加熱により分解してラジカルを発生し、(B)成分同士、又は(A)成分及び(B)成分の重合反応を促進する化合物が好ましい。
(I)成分は分解点が、110℃以上200℃以下の化合物が好ましく、より低温で重合反応を促進する観点から、110℃以上175℃以下の化合物がより好ましい。
(J)成分としては、N-メチル-2-ピロリドン、γ-ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、酢酸ベンジル、n-ブチルアセテート、エトキシエチルプロピオネート、3-メチルメトキシプロピオネート、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホリルアミド、テトラメチレンスルホン、シクロヘキサノン、シクロペンタノン、ジエチルケトン、ジイソブチルケトン、メチルアミルケトン、N-ジメチルモルホリン等が挙げられ、通常、他の成分を充分に溶解できるものであれば特に制限はない。
この中でも、各成分の溶解性と感光性樹脂膜形成時の塗布性に優れる観点から、N-メチル-2-ピロリドン、γ-ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドを用いることが好ましい。
式(21)で表される化合物は、3-メトキシ-N,N-ジメチルプロパンアミド(例えば、商品名「KJCMPA-100」(KJケミカルズ株式会社製))であることが好ましい。
(J)成分の含有量は、特に限定されないが、一般的に、(A)成分100質量部に対して、50~1000質量部である。
本発明の感光性樹脂組成物の、例えば、80質量%以上、90質量%以上、95質量%以上、98質量%以上又は100質量%が、(J)成分を除いて、
(A)~(D)成分、
(A)~(I)成分、又は
(A)~(D)成分、並びに任意に(E)~(I)成分、界面活性剤、及びレベリング剤からなっていてもよい。
本発明の硬化物は、パターン硬化物として用いてもよく、パターンがない硬化物として用いてもよい。
本発明の硬化物の膜厚は、5~20μmが好ましい。
アスペクト比は、例えば、走査型電子顕微鏡(SEM)によりパターン硬化物の断面を撮影し、画像から膜厚と開口幅を測定し、以下の式に従って算出することができる。
アスペクト比=(硬化後膜厚/基板上の開口幅)
これにより、パターン硬化物を得ることができる。
乾燥温度は90~150℃が好ましく、溶解コントラスト確保の観点から、90~120℃がより好ましい。
乾燥時間は、30秒間~5分間が好ましい。
乾燥は、2回以上行ってもよい。
これにより、上述の感光性樹脂組成物を膜状に形成した感光性樹脂膜を得ることができる。
照射する活性光線は、i線等の紫外線、可視光線、放射線等が挙げられるが、i線であることが好ましい。
露光装置としては、平行露光機、投影露光機、ステッパ、スキャナ露光機等を用いることができる。
現像液として用いる有機溶剤は、現像液としては、感光性樹脂膜の良溶媒を単独で、又は良溶媒と貧溶媒を適宜混合して用いることができる。
良溶媒としては、N-メチル-2-ピロリドン、N-アセチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
貧溶媒としては、トルエン、キシレン、メタノール、エタノール、イソプロパノール、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、水等が挙げられる。
現像時間は、用いる(A)成分によっても異なるが、10秒間~15分間が好ましく、10秒間~5分間がより好ましく、生産性の観点からは、20秒間~5分間がさらに好ましい。
リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール、トルエン、キシレン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル等を単独又は適宜混合して用いてもよく、また段階的に組み合わせて用いてもよい。
(A)成分のポリイミド前駆体が、加熱処理工程によって、脱水閉環反応を起こし、通常対応するポリイミドとなる。
上記範囲内であることにより、基板やデバイスへのダメージを小さく抑えることができ、デバイスを歩留り良く生産することが可能となり、プロセスの省エネルギー化を実現することができる。
上記範囲内であることにより、架橋反応又は脱水閉環反応を充分に進行することができる。
加熱処理の雰囲気は大気中であっても、窒素等の不活性雰囲気中であってもよいが、パターン樹脂膜の酸化を防ぐことができる観点から、窒素雰囲気下が好ましい。
上記パッシベーション膜、バッファーコート膜、層間絶縁膜、カバーコート層及び表面保護膜等からなる群から選択される1以上を用いて、信頼性の高い、半導体装置、多層配線板、各種電子デバイス、積層デバイス(マルチダイファンアウトウエハレベルパッケージ等)等の電子部品などを製造することができる。
図1は、本発明の一実施形態に係る電子部品である多層配線構造の半導体装置の製造工程図である。
図1において、回路素子を有するSi基板等の半導体基板1は、回路素子の所定部分を除いてシリコン酸化膜等の保護膜2等で被覆され、露出した回路素子上に第1導体層3が形成される。その後、前記半導体基板1上に層間絶縁膜4が形成される。
次いで、窓6Bから露出した第1導体層3を腐食することなく、感光性樹脂層5のみを腐食するようなエッチング溶液を用いて感光性樹脂層5が完全に除去される。
3層以上の多層配線構造を形成する場合には、上述の工程を繰り返して行い、各層を形成することができる。
尚、前記例において、層間絶縁膜を本発明の感光性樹脂組成物を用いて形成することも可能である。
A1:後述の合成例1で得られた化合物
A2:後述の合成例2で得られた化合物
A3:後述の合成例3で得られた化合物
A4:後述の合成例4で得られた化合物
B1:A-DCP(新中村化学工業株式会社製、トリシクロデカンジメタノールジアクリレート、下記式で表される化合物)
B3:TEGDMA(新中村化学工業株式会社製、テトラエチレングリコールジメタクリレート)
B4:A-TMMT(新中村化学工業株式会社製、ペンタエリスリトールテトラアクリレート)
C1:IRGACURE OXE 02(BASFジャパン株式会社製、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム))
C2:G-1820(PDO)(Lambson株式会社製、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシム)
C3:NCI-930(株式会社ADEKA製、2-(アセトキシイミノ)-1-[4-[4-(2-ヒドロキシエトキシ)フェニルスルファニル]フェニル]プロパン-1-オン)
D1:アデカスタブ LA-29(株式会社ADEKA製、2-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール)
D2:アデカスタブ LA-24(株式会社ADEKA製、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール)
D3:アデカスタブ LA-32(株式会社ADEKA製、2-(2H-ベンゾトリアゾール-2-イル)-p-クレゾール)
D4:SEESORB106(シプロ化成株式会社製、2,2′,4,4′-テトラヒドロキシベンゾフェノン)
D5:SEESORB107(シプロ化成株式会社製、2,2′-ジヒドロキシ-4,4′-ジメトキシベンゾフェノン)
D6:ディスパースレッド1(日立化成テクノサービス株式会社製、4-[エチル(2-ヒドロキシエチル)アミノ]-4′-ニトロアゾベンゼン)
D7:クルクミン(株式会社三和ケミカル製、(1E,6E)-1,7-ビス(4-ヒドロキシ-3-メトキシフェニル)-1,6-ヘプタジエン-3,5-ジオン)
D8:HPH(株式会社三和ケミカル製、1,7-ビス(4-ヒドロキシフェニル)-1,6-ヘプタジエン-3,5-ジオン)
E1:Taobn(Hampford Research社製、1,4,4-トリメチル-2,3-ジアザビシクロ[3.2.2]-ノナ-2-エン-2,3-ジキソイド)
E2:ヒドロキノン
H1:EMK(Aldrich社製、4,4′-ビス(ジエチルアミノ)ベンゾフェノン)
I1:パークミルD(日油株式会社製、ビス(1-フェニル-1-メチルエチル)ペルオキシド)
J1:N-メチル-2-ピロリドン
J2:γ-ブチロラクトン
J3:KJCMPA-100(KJケミカルズ株式会社製、3-メトキシ-N,N-ジメチルプロパンアミド)
D1~D8をそれぞれクロロホルムに溶かし、10mg/Lになるよう調製し、測定用試料とした。
測定機器:U-3900H(株式会社日立ハイテクサイエンス製)
測定条件:セル長:10.0mm
3,3′,4,4′-ジフェニルエーテルテトラカルボン酸二無水物(ODPA)47.1g(152mmol)とメタクリル酸2-ヒドロキシエチル(HEMA)5.54g(43mmol)及び触媒量の1,4-ジアザビシクロ[2.2.2.]オクタントリエチレンジアミンを380gのN-メチル-2-ピロリドン(NMP)中に溶解して、45℃で1時間撹拌した後25℃まで冷却し、2,2’-ジメチルベンジジン27.4g(129mmol)及び乾燥したN-メチル-2-ピロリドン145mLを加えた後45℃で150分間撹拌した後、室温へ冷却した。この溶液へトリフルオロ酢酸無水物59.7g(284mmol)を滴下した後、120分間撹拌した後、触媒量のベンゾキノンを加え、さらにHEMA40.4g(310mmol)を加え45℃で20時間撹拌した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A1を得た。
ゲルパーミエーションクロマトグラフ(GPC)法を用いて、標準ポリスチレン換算により、以下の条件で、重量平均分子量を求めた。A1の重量平均分子量は35,000であった。
ポンプ:株式会社日立製作所製L6000
株式会社島津製作所製C-R4A Chromatopac
測定条件:カラムGelpack GL-S300MDT-5×2本
溶離液:THF/DMF=1/1(容積比)
LiBr(0.03mol/L)、H3PO4(0.06mol/L)
流速:1.0mL/min、検出器:UV270nm
磁場強度:400MHz
基準物質:テトラメチルシラン(TMS)
溶媒:ジメチルスルホキシド(DMSO)
ODPA47.1g(152mmol)とHEMA2.77g(21mmol)及び触媒量の1,4-ジアザビシクロ[2.2.2.]オクタントリエチレンジアミンを500gのNMP中に溶解して、45℃で1時間撹拌した後25℃まで冷却し、2,2’-ジメチルベンジジン30.0g(141mmol)及び乾燥したNMP145mLを加えた後45℃で150分間撹拌した後、室温へ冷却した。この溶液へトリフルオロ酢酸無水物65.2g(311mmol)を滴下した後、180分間撹拌した後、触媒量のベンゾキノンを加え、さらにHEMA43.1g(331mmol)を加え45℃で20時間撹拌した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A2を得た。
ゲルパーミエーションクロマトグラフ(GPC)法を用いて、標準ポリスチレン換算により、合成例1と同じ条件で、重量平均分子量を求めた。A2の重量平均分子量は70,000であった。
ODPA62.0g(200mmol)、HEMA5.2g(40.0mmol)及び触媒量の1,4-ジアザビシクロ[2.2.2]オクタントリエチレンジアミンをNMP250gに溶解し、45℃で1時間撹拌した後、25℃まで冷却し、m-フェニレンジアミン5.5g(50.9mmol)、オキシジアニリン(4,4′-ジアミノジフェニルエーテル)23.8g(119mmol)及び乾燥したNMP100mLを加え、45℃で150分間撹拌した後、室温へ冷却した。この溶液へトリフルオロ酢酸無水物78.5g(374mmol)を滴下し、20分間撹拌した後、HEMA53.1g(408mmol)を加え45℃で20時間撹拌した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A3を得た。
GPC法を用いて、合成例1と同じ条件で、重量平均分子量を求めた。A3の重量平均分子量は35,000であった。
また、A3のエステル化率を、合成例1と同じ条件でNMR測定を行い、算出した。エステル化率は、ポリアミド酸の全カルボキシ基に対し(全カルボキシ基及び全カルボキシエステルに対し)70モル%であった(残り30モル%はカルボキシ基)。
ピロメリット酸二無水物(PMDA)43.6g(200mmol)とHEMA54.9g(401mmol)とヒドロキノン0.220gをNMP394gに溶解し、1,8-ジアザビシクロウンデセンを触媒量添加した後に、25℃で24時間撹拌し、エステル化を行い、ピロメリット酸-ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をPMDA-HEMA溶液とする。
ODPA49.6g(160mmol)とHEMA4.98g(328mmol)とヒドロキノン0.176gをNMP378gに溶解し、1,8-ジアザビシクロウンデセンを触媒量添加した後に、25℃で48時間撹拌し、エステル化を行い、3,3′,4,4′-ジフェニルエーテルテトラカルボン酸-ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をODPA-HEMA溶液とする。
PMDA-HEMA溶液196gとODPA-HEMA溶液58.7gとを混合し、その後、氷冷下で塩化チオニル25.9g(218mmol)を反応溶液温度が10℃以下を保つように滴下漏斗を用いて滴下した。塩化チオニルの滴下が終了した後、氷冷下で2時間反応を行いPMDAとODPAの酸クロリドの溶液を得た。次いで、滴下漏斗を用いて、2,2′-ビス(トリフルオロメチル)ベンジジン31.7g(99.0mmol)、ピリジン34.5g(436mmol)、ヒドロキノン0.076g(693mmol)のNMP90.2g溶液を氷冷下で反応溶液の温度が10℃を超えないように注意しながら滴下した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A4を得た。
GPC法を用いて、合成例1と同じ条件で、重量平均分子量を求めた。A4の重量平均分子量は34,000であった。
また、A4のエステル化率を、合成例1と同じ条件でNMR測定を行い、算出した。エステル化率は、ポリアミド酸の全カルボキシ基に対し(全カルボキシ基及び全カルボキシエステルに対し)97モル%であった(残り3モル%はカルボキシ基)。
[感光性樹脂組成物の調製]
表2及び表3に示した成分及び配合量にて、実施例1~24及び比較例1~7の感光性樹脂組成物を調製した。表2及び表3の配合量は、100質量部の(A)成分に対する、各成分の質量部である。
得られた感光性樹脂組成物を、塗布装置Act8(東京エレクトロン株式会社製)を用いて、シリコンウエハ上にスピンコートし、100℃で2分間乾燥後、110℃で2分間乾燥して乾燥膜厚が7~10μmの感光性樹脂膜を形成した。
得られた感光性樹脂膜をシクロペンタノンに浸漬して完全に溶解するまでの時間の2倍を現像時間として設定した。
また、上記と同様に感光性樹脂膜を作製し、得られた感光性樹脂膜に、i線ステッパFPA-3000iW(キヤノン株式会社製)を用いて、表2及び表3に示した露光量で、直径1μm~100μmのビア形成用フォトマスクに照射して、露光を行った。
Act8を用いて、大気下、120℃で3分間、露光後加熱を行った。
露光後加熱後の樹脂膜を、Act8を用いて、シクロペンタノンに、上記の現像時間でパドル現像した後、プロピレングリコールモノメチルエーテルアセテート(PGMEA)でリンス洗浄を行い、パターン樹脂膜を得た。
得られたパターン樹脂膜を、縦型拡散炉μ-TF(光洋サーモシステム株式会社製)を用いて、窒素雰囲気下、175℃で1時間加熱し、パターン硬化物(硬化後膜厚5μm)を得た。
得られたパターン硬化物について、光学顕微鏡を用いて観察し、ビアのマスク寸法の面積に対して、55%以上の基板表面が露出した開口が形成された最小の直径を解像度として、以下の基準で評価した。
A:4μm未満のパターンが開口した。
B:4μm以上6μm未満のパターンが開口した。
C:6μm以上8μm未満のパターンが開口した。
D:8μm以上のパターンが開口した。
結果を表2及び表3に示す。
得られたパターン硬化物について、断面観察を集束イオンビーム加工、走査型電子顕微鏡複合装置(FIB-SEM)SMI500(株式会社日立ハイテクサイエンス製)を用いて行った。
得られた断面画像から、硬化後膜厚と、基板上の開口幅を測定した。下記式に従ってアスペクト比を算出した。
アスペクト比=(硬化後膜厚/基板上の開口幅)
結果を表2及び表3に示す。
[感光性樹脂組成物の調製]
表4に示した成分及び配合量にて、実施例5a、6a、10a、20a~23a及び比較例1a~4a、7a、8aの感光性樹脂組成物を調製した。表4の配合量は、100質量部の(A)成分に対する、各成分の質量部である。
得られた感光性樹脂組成物を用いて、実施例1~24及び比較例1~7と同様にして、感光性樹脂膜を形成した。
得られた感光性樹脂膜をシクロペンタノンに浸漬して完全に溶解するまでの時間の2倍を現像時間として設定した。
また、上記と同様に感光性樹脂膜を作製し、得られた感光性樹脂膜に、FPA-3000iWを用いて、表4に示した露光量で、直径1μm~100μmのビア形成用フォトマスクに照射して、露光を行った。
露光後の樹脂膜を、Act8を用いて、シクロペンタノンに、上記の現像時間でパドル現像した後、PGMEAでリンス洗浄を行い、パターン樹脂膜を得た。
得られたパターン樹脂膜を、μ-TFを用いて、窒素雰囲気下、175℃で1時間加熱し、パターン硬化物(硬化後膜厚5μm)を得た。
得られたパターン硬化物について、実施例1~24及び比較例1~7と同様にして、解像度を評価した。
結果を表4に示す。
得られたパターン硬化物について、実施例1~24及び比較例1~7と同様にして、アスペクト比を算出した。
結果を表4に示す。
[感光性樹脂組成物の調製]
表5に示した成分及び配合量にて、実施例25~27及び比較例8~10の感光性樹脂組成物を調製した。表5の配合量は、100質量部の(A)成分に対する、各成分の質量部である。
得られた感光性樹脂組成物を、Act8を用いて、シリコンウエハ上にスピンコートし、100℃で2分間乾燥後、110℃で2分間乾燥して乾燥膜厚が12~15μmの感光性樹脂膜を形成した。
得られた感光性樹脂膜をシクロペンタノンに浸漬して完全に溶解するまでの時間の2倍を現像時間として設定した。
また、上記と同様に感光性樹脂膜を作製し、得られた感光性樹脂膜に、FPA-3000iWを用いて、表5に示した露光量で、直径1μm~100μmのビア形成用フォトマスクに照射して、露光を行った。
露光後の樹脂膜を、Act8を用いて、シクロペンタノンに、上記の現像時間でパドル現像した後、PGMEAでリンス洗浄を行い、パターン樹脂膜を得た。
得られたパターン樹脂膜を、μ-TFを用いて、窒素雰囲気下、175℃で1時間加熱し、パターン硬化物(硬化後膜厚10μm)を得た。
得られたパターン硬化物について、光学顕微鏡を用いて観察し、ビアのマスク寸法の面積に対して、55%以上の基板表面が露出した開口が形成された最小の直径を解像度として、以下の基準で評価した。
A:8μm未満のパターンが開口した。
B:8μm以上10μm未満のパターンが開口した。
C:10μm以上15μm未満のパターンが開口した。
D:15μm以上のパターンが開口した。
結果を表5に示す。
[アスペクト比の評価]
得られたパターン硬化物について、実施例1~24及び比較例1~7と同様にして、アスペクト比を算出した。
結果を表5に示す。
[感光性樹脂組成物の調製]
表6に示した成分及び配合量にて、実施例28、29及び比較例11、12の感光性樹脂組成物を調製した。表6の配合量は、100質量部の(A)成分に対する、各成分の質量部である。
得られた感光性樹脂組成物を、Act8を用いて、シリコンウエハ上にスピンコートし、100℃で2分間乾燥後、110℃で2分間乾燥して乾燥膜厚が12~15μmの感光性樹脂膜を形成した。
得られた感光性樹脂膜をシクロペンタノンに浸漬して完全に溶解するまでの時間の2倍を現像時間として設定した。
また、上記と同様に感光性樹脂膜を作製し、得られた感光性樹脂膜に、FPA-3000iWを用いて、表6に示した露光量で、直径1μm~100μmのビア形成用フォトマスクに照射して、露光を行った。
Act8を用いて、大気下、120℃で3分間、露光後加熱を行った。
露光後加熱後の樹脂膜を、Act8を用いて、シクロペンタノンに、上記の現像時間でパドル現像した後、PGMEAでリンス洗浄を行い、パターン樹脂膜を得た。
得られたパターン樹脂膜を、μ-TFを用いて、窒素雰囲気下、175℃で1時間加熱し、パターン硬化物(硬化後膜厚10μm)を得た。
この明細書に記載の文献、及び本願のパリ条約による優先権の基礎となる出願の内容を全て援用する。
Claims (18)
- (A)重合性の不飽和結合を有するポリイミド前駆体、
(B)重合性モノマー、
(C)光重合開始剤、及び
(D)紫外線吸収剤を含有する感光性樹脂組成物。 - 前記(A)成分が、下記式(1)で表される構造単位を有するポリイミド前駆体である請求項1に記載の感光性樹脂組成物。
(式(1)中、X1は1以上の芳香族基を有する4価の基であって、-COOR1基と-CONH-基とは互いにオルト位置にあり、-COOR2基と-CO-基とは互いにオルト位置にある。Y1は1以上の芳香族基を有する2価の基である。R1及びR2は、それぞれ独立に、水素原子、下記式(2)で表される基、又は炭素数1~4の脂肪族炭化水素基であり、R1及びR2の少なくとも一方が前記式(2)で表される基である。)
(式(2)中、R3~R5は、それぞれ独立に、水素原子又は炭素数1~3の脂肪族炭化水素基であり、mは1~10の整数である。) - 前記(B)成分が、重合性の不飽和二重結合を含む基を有する重合性モノマーを含む請求項1又は2に記載の感光性樹脂組成物。
- 前記重合性の不飽和二重結合を含む基が、2以上である請求項3に記載の感光性樹脂組成物。
- 前記重合性モノマーが、脂肪族環状骨格を有する請求項1~4のいずれかに記載の感光性樹脂組成物。
- n1+n2が、2又は3である請求項6に記載の感光性樹脂組成物。
- 前記(D)成分が、10mg/Lの濃度で、365nmにおける吸光度が0.1以上である請求項1~8のいずれかに記載の感光性樹脂組成物。
- 前記(D)成分が、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、アゾベンゼン系化合物、及びポリフェノール系化合物からなる群から選択される1以上である請求項1~9のいずれかに記載の感光性樹脂組成物。
- 前記(D)成分が、2-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール、2-(2H-ベンゾトリアゾール-2-イル)-p-クレゾール、2,2′,4,4′-テトラヒドロキシベンゾフェノン、2,2′-ジヒドロキシ-4,4′-ジメトキシベンゾフェノン、4-[エチル(2-ヒドロキシエチル)アミノ]-4′-ニトロアゾベンゼン、(1E,6E)-1,7-ビス(4-ヒドロキシ-3-メトキシフェニル)-1,6-ヘプタジエン-3,5-ジオン、及び1,7-ビス(4-ヒドロキシフェニル)-1,6-ヘプタジエン-3,5-ジオンからなる群から選択される1以上である請求項1~10のいずれかに記載の感光性樹脂組成物。
- さらに、(I)熱重合開始剤を含む請求項1~11のいずれかに記載の感光性樹脂組成物。
- 請求項1~12のいずれかに記載の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて、現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、を含むパターン硬化物の製造方法。 - 前記加熱処理の温度が200℃以下である請求項13に記載のパターン硬化物の製造方法。
- 請求項1~12のいずれかに記載の感光性樹脂組成物を硬化した硬化物。
- パターン硬化物である請求項15に記載の硬化物。
- 請求項15又は16に記載の硬化物を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
- 請求項17に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201980065275.4A CN113196170B (zh) | 2018-10-03 | 2019-06-17 | 感光性树脂组合物、图案固化物的制造方法、固化物、层间绝缘膜、覆盖涂层、表面保护膜及电子部件 |
| JP2020549956A JPWO2020070924A1 (ja) | 2018-10-03 | 2019-06-17 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| KR1020217008587A KR20210068417A (ko) | 2018-10-03 | 2019-06-17 | 감광성 수지 조성물, 패턴 경화물의 제조 방법, 경화물, 층간 절연막, 커버 코트층, 표면 보호막 및 전자 부품 |
| US17/282,457 US20210382391A1 (en) | 2018-10-03 | 2019-06-17 | Photosensitive resin composition, method for manufacturing patterned cured product, cured product, interlayer insulating film, cover coat layer, surface protective film, and electronic component |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-188703 | 2018-10-03 | ||
| JP2018188703 | 2018-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020070924A1 true WO2020070924A1 (ja) | 2020-04-09 |
Family
ID=70055471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2019/023925 Ceased WO2020070924A1 (ja) | 2018-10-03 | 2019-06-17 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20210382391A1 (ja) |
| JP (1) | JPWO2020070924A1 (ja) |
| KR (1) | KR20210068417A (ja) |
| CN (1) | CN113196170B (ja) |
| TW (1) | TWI847987B (ja) |
| WO (1) | WO2020070924A1 (ja) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021167926A (ja) * | 2020-04-13 | 2021-10-21 | 昭和電工マテリアルズ株式会社 | 感光性樹脂組成物、それを用いた硬化物、パターン硬化物の製造方法及び電子部品の製造方法 |
| JP2021173787A (ja) * | 2020-04-20 | 2021-11-01 | 旭化成株式会社 | 感光性樹脂組成物、硬化レリーフパターンの製造方法、硬化レリーフパターン、半導体装置及び表示体装置 |
| JP2022110710A (ja) * | 2021-01-19 | 2022-07-29 | Hdマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| WO2025159143A1 (ja) * | 2024-01-25 | 2025-07-31 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI817316B (zh) * | 2021-01-12 | 2023-10-01 | 日商旭化成股份有限公司 | 聚醯亞胺前驅體樹脂組合物及其製造方法 |
| JP2023160771A (ja) * | 2022-04-21 | 2023-11-02 | 旭化成株式会社 | 感光性樹脂組成物及び硬化レリーフパターンの製造方法 |
| CN118605083B (zh) * | 2024-06-07 | 2025-03-07 | 上海镭利电子材料有限公司 | 一种干膜型感光性树脂组合物及其制备方法和应用 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008070897A (ja) * | 2007-10-29 | 2008-03-27 | Hitachi Chemical Dupont Microsystems Ltd | 感光性ポリイミド前駆体組成物及びそれを用いたパターンの製造法 |
| JP2009037232A (ja) * | 2007-07-09 | 2009-02-19 | Jsr Corp | 感光性ペースト組成物およびパターン形成方法 |
| JP2010117614A (ja) * | 2008-11-14 | 2010-05-27 | Toray Ind Inc | 感光性組成物及びそれを用いた感光性グリーンシートならびにセラミックス多層基板 |
| WO2014097595A1 (ja) * | 2012-12-21 | 2014-06-26 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 |
| JP2015219491A (ja) * | 2014-05-21 | 2015-12-07 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体、該ポリイミド前駆体を含む感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 |
| JP2016199662A (ja) * | 2015-04-09 | 2016-12-01 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体を含む樹脂組成物、それを用いた硬化膜及びパターン硬化膜の製造方法、並びに電子部品 |
| JP2018084626A (ja) * | 2016-11-22 | 2018-05-31 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| WO2019058882A1 (ja) * | 2017-09-19 | 2019-03-28 | 富士フイルム株式会社 | パターン形成用組成物、膜、赤外線カットフィルタ、赤外線透過フィルタ、固体撮像素子、赤外線センサ、及び、カメラモジュール |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3666839B2 (ja) * | 1998-01-23 | 2005-06-29 | 東京応化工業株式会社 | ポジ型ホトレジスト組成物およびその製造方法 |
| JP2008111470A (ja) | 2006-10-30 | 2008-05-15 | Nissan Motor Co Ltd | 無段変速機のモード切り替え時変速制御装置 |
| JP5169446B2 (ja) | 2008-04-28 | 2013-03-27 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、該樹脂組成物を用いたポリベンゾオキサゾール膜、パターン硬化膜の製造方法及び電子部品 |
| US9005853B2 (en) * | 2010-05-20 | 2015-04-14 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive film, rib pattern formation method, hollow structure and formation method for same, and electronic component |
| KR102058349B1 (ko) * | 2012-07-09 | 2019-12-23 | 도레이 카부시키가이샤 | 감광성 수지 조성물, 도전성 배선 보호막 및 터치 패널 부재 |
| JPWO2014092002A1 (ja) * | 2012-12-14 | 2017-01-12 | 旭硝子株式会社 | 硬化性樹脂組成物、およびそれを用いた積層体とその製造方法 |
| WO2014097594A1 (ja) * | 2012-12-21 | 2014-06-26 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体樹脂組成物 |
| WO2015012228A1 (ja) * | 2013-07-25 | 2015-01-29 | 東レ株式会社 | タッチパネル用ネガ型感光性白色組成物、タッチパネル及びタッチパネルの製造方法 |
| JP5542236B1 (ja) | 2013-09-06 | 2014-07-09 | 株式会社野村総合研究所 | クーポン管理システムおよびクーポン管理プログラム |
| CN105829968B (zh) * | 2013-10-09 | 2020-03-27 | 日立化成杜邦微系统股份有限公司 | 包含聚酰亚胺前体的树脂组合物和使用其的固化膜的制造方法 |
| JPWO2016084855A1 (ja) * | 2014-11-26 | 2017-08-31 | 日立化成株式会社 | 感光性樹脂組成物、感光性エレメント、硬化物、半導体装置、レジストパターンの形成方法及び回路基材の製造方法 |
| WO2018003726A1 (ja) * | 2016-06-29 | 2018-01-04 | 富士フイルム株式会社 | ネガ型感光性樹脂組成物、硬化膜、硬化膜の製造方法、半導体デバイス、積層体の製造方法、半導体デバイスの製造方法およびポリイミド前駆体 |
-
2019
- 2019-06-17 WO PCT/JP2019/023925 patent/WO2020070924A1/ja not_active Ceased
- 2019-06-17 KR KR1020217008587A patent/KR20210068417A/ko not_active Ceased
- 2019-06-17 CN CN201980065275.4A patent/CN113196170B/zh active Active
- 2019-06-17 JP JP2020549956A patent/JPWO2020070924A1/ja active Pending
- 2019-06-17 US US17/282,457 patent/US20210382391A1/en active Pending
- 2019-07-03 TW TW108123373A patent/TWI847987B/zh active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009037232A (ja) * | 2007-07-09 | 2009-02-19 | Jsr Corp | 感光性ペースト組成物およびパターン形成方法 |
| JP2008070897A (ja) * | 2007-10-29 | 2008-03-27 | Hitachi Chemical Dupont Microsystems Ltd | 感光性ポリイミド前駆体組成物及びそれを用いたパターンの製造法 |
| JP2010117614A (ja) * | 2008-11-14 | 2010-05-27 | Toray Ind Inc | 感光性組成物及びそれを用いた感光性グリーンシートならびにセラミックス多層基板 |
| WO2014097595A1 (ja) * | 2012-12-21 | 2014-06-26 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 |
| JP2015219491A (ja) * | 2014-05-21 | 2015-12-07 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体、該ポリイミド前駆体を含む感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 |
| JP2016199662A (ja) * | 2015-04-09 | 2016-12-01 | 日立化成デュポンマイクロシステムズ株式会社 | ポリイミド前駆体を含む樹脂組成物、それを用いた硬化膜及びパターン硬化膜の製造方法、並びに電子部品 |
| JP2018084626A (ja) * | 2016-11-22 | 2018-05-31 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| WO2019058882A1 (ja) * | 2017-09-19 | 2019-03-28 | 富士フイルム株式会社 | パターン形成用組成物、膜、赤外線カットフィルタ、赤外線透過フィルタ、固体撮像素子、赤外線センサ、及び、カメラモジュール |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021167926A (ja) * | 2020-04-13 | 2021-10-21 | 昭和電工マテリアルズ株式会社 | 感光性樹脂組成物、それを用いた硬化物、パターン硬化物の製造方法及び電子部品の製造方法 |
| JP7524587B2 (ja) | 2020-04-13 | 2024-07-30 | 株式会社レゾナック | 感光性樹脂組成物、それを用いた硬化物、パターン硬化物の製造方法及び電子部品の製造方法 |
| JP2021173787A (ja) * | 2020-04-20 | 2021-11-01 | 旭化成株式会社 | 感光性樹脂組成物、硬化レリーフパターンの製造方法、硬化レリーフパターン、半導体装置及び表示体装置 |
| JP7530736B2 (ja) | 2020-04-20 | 2024-08-08 | 旭化成株式会社 | 感光性樹脂組成物、硬化レリーフパターンの製造方法、硬化レリーフパターン、半導体装置及び表示体装置 |
| JP2022110710A (ja) * | 2021-01-19 | 2022-07-29 | Hdマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| JP7639354B2 (ja) | 2021-01-19 | 2025-03-05 | Hdマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
| WO2025159143A1 (ja) * | 2024-01-25 | 2025-07-31 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113196170A (zh) | 2021-07-30 |
| KR20210068417A (ko) | 2021-06-09 |
| TW202028861A (zh) | 2020-08-01 |
| JPWO2020070924A1 (ja) | 2021-09-24 |
| CN113196170B (zh) | 2025-10-21 |
| US20210382391A1 (en) | 2021-12-09 |
| TWI847987B (zh) | 2024-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7616311B2 (ja) | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| TWI847987B (zh) | 感光性樹脂組成物、圖案硬化物的製造方法、硬化物、層間絕緣膜、面塗層、表面保護膜及電子零件 | |
| JP7395817B2 (ja) | パターン硬化膜の製造方法、感光性樹脂組成物、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7147749B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7355025B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| KR102762481B1 (ko) | 감광성 수지 조성물, 패턴 경화물의 제조 방법, 경화물, 층간 절연막, 커버 코트층, 표면 보호막 및 전자 부품 | |
| WO2020071201A1 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7238316B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7459797B2 (ja) | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| WO2021215374A1 (ja) | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7639354B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JPWO2018179330A1 (ja) | 感光性樹脂組成物、パターン硬化膜の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜、及び電子部品 | |
| JP7243233B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7225652B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 | |
| JP7009803B2 (ja) | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19869525 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2020549956 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19869525 Country of ref document: EP Kind code of ref document: A1 |
|
| WWR | Wipo information: refused in national office |
Ref document number: 1020217008587 Country of ref document: KR |
|
| WWC | Wipo information: continuation of processing after refusal or withdrawal |
Ref document number: 1020217008587 Country of ref document: KR |
|
| WWG | Wipo information: grant in national office |
Ref document number: 201980065275.4 Country of ref document: CN |