WO2018150771A1 - Photosensitive resin composition, cured film and production method therefor, and electronic component - Google Patents
Photosensitive resin composition, cured film and production method therefor, and electronic component Download PDFInfo
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- WO2018150771A1 WO2018150771A1 PCT/JP2018/000642 JP2018000642W WO2018150771A1 WO 2018150771 A1 WO2018150771 A1 WO 2018150771A1 JP 2018000642 W JP2018000642 W JP 2018000642W WO 2018150771 A1 WO2018150771 A1 WO 2018150771A1
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a photosensitive resin composition suitably used for forming a surface protective film, an interlayer insulating film, and the like of an electronic component, and further, a cured film formed from the composition, a method for producing the same, and the curing
- the present invention relates to an electronic component having a film.
- a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin has a problem that it is difficult to achieve both chemical resistance and crack resistance of a cured film obtained from the photosensitive resin composition. It is estimated that the reason is as follows. For example, if only an epoxy-based crosslinking agent is used to crosslink a resin having a phenolic hydroxyl group, a hydroxyl group is generated due to the opening of an epoxy ring in the crosslinking reaction. If only a methylol-based crosslinking agent is used, a phenolic compound is generated even after the crosslinking reaction. Since the hydroxyl group remains, chemical resistance deteriorates.
- the present invention includes, for example, the following [1] to [8].
- [1] A photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C).
- the crosslinking agent (D) is an epoxy crosslinking agent (D1) and a group represented by —CH 2 OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or carbon
- the manufacturing method of the cured film which has the process of developing a film
- both chemical resistance and crack resistance of a cured film obtained from a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin can be achieved.
- FIG. 1 shows the storage elastic modulus (E ′) of the cured films of Examples and Comparative Examples.
- FIG. 2 shows the storage elastic modulus (E ′) of the cured film of the example.
- FIG. 3 shows the storage elastic modulus (E ′) of the cured film of the example.
- FIG. 4 shows the storage elastic modulus (E ′) of the cured film of the comparative example.
- the photosensitive resin composition of the present invention contains a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C) described below.
- the resin (A) having a phenolic hydroxyl group examples include a polymer (a1) having a structural unit derived from a radical polymerizable monomer having a phenolic hydroxyl group (hereinafter also referred to as “polymer (a1)”), a novolac resin. (A2), polybenzoxazole precursor (a3), polyimide having a phenolic hydroxyl group, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin.
- the polymer (a1), the novolak resin (a2), and the polybenzoxazole precursor (a3) are preferable, and the polymer (a1) is more preferable.
- Resin (A) can be used by 1 type, or can be used in combination of 2 or more type.
- Polymer (a1) examples include a radical polymerizable monomer having a phenolic hydroxyl group alone or a copolymer, and a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer. .
- radical polymerizable monomer having a phenolic hydroxyl group examples include hydroxystyrene such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol.
- Monomers Monomers formed by substituting one or more hydrogen atoms bonded to the aromatic ring carbon of hydroxystyrene monomers with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano; vinyl hydroquinone, 5-vinyl pyrogallol, 6- Vinyl pyrogallol is mentioned.
- the monomer which protects the phenolic hydroxyl group of the said monomer with an alkyl group, a silyl group, etc. can also be mentioned.
- the monomer which protects the said phenolic hydroxyl group it can be set as the polymer (a1) which has a phenolic hydroxyl group by removing the said protection after forming a polymer.
- the said monomer can be used by 1 type, or can be used in combination of 2 or more type.
- radical polymerizable monomers examples include styrene monomers such as styrene, ⁇ -methyl styrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; aromatic rings of styrene monomers Monomers formed by substituting one or more hydrogen atoms bonded to carbon with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano; dienes such as butadiene, isoprene, chloroprene; unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and An unsaturated carboxylic acid such as a half ester; o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, or one or more hydrogen atoms bonded to the aromatic ring carbon
- the content ratio of the structural unit derived from the radical polymerizable monomer having a phenolic hydroxyl group is derived from the structural unit derived from the radical polymerizable monomer having a phenolic hydroxyl group and the other radical polymerizable monomer. It is preferably 30 mol% or more, more preferably 40 to 95 mol%, with respect to a total content of 100 mol% with the structural unit.
- poly-p-hydroxystyrene poly-p-hydroxystyrene, m-hydroxystyrene / p-hydroxystyrene copolymer, p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / p- Vinyl benzyl glycidyl ether / styrene copolymer, p-hydroxystyrene / (3,4-epoxycyclohexyl) methyl methacrylate copolymer, p-hydroxystyrene / (3,4-epoxycyclohexyl) methyl methacrylate / styrene copolymer, etc.
- the hydroxy styrene-type polymer of this is mentioned.
- the novolac resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst.
- phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl
- aldehydes include formaldehyde, para
- the novolak resin (a2) include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, a cresol / salicylaldehyde condensed novolak resin, a phenol-naphthol / formaldehyde condensed novolak resin, a novolac resin, and the like.
- a resin modified with a rubber-like polymer having a polymerizable vinyl group for example, a resin described in JP 2010-015101 A).
- Polybenzoxazole precursor (a3) As a polybenzoxazole precursor (a3), the polymer which has a structural unit shown to Formula (1) is mentioned, for example.
- the polybenzoxazole precursor (a3) may be a polymer having one type of structural unit or a polymer having two or more types of structural units.
- X is a divalent organic group
- Y is a tetravalent aromatic ring-containing group
- N and OH bonded to Y form a pair
- N and OH of each pair are the same aromatic ring Bonded to the adjacent carbon atom above.
- the divalent organic group represented by X for example, halogenated carbon atoms and optionally 6-20 arylene group, the formula (g1): - Ar 1 -R 1 -Ar 1 - a divalent represented Groups, alkanediyl groups having 1 to 10 carbon atoms, and cycloalkanediyl groups having 3 to 20 carbon atoms.
- Ar 1 is each independently an arylene group having 6 to 20 carbon atoms which may be halogenated
- R 1 is a direct bond or a divalent group.
- the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and an optionally halogenated alkanediyl group.
- Examples of the arylene group having 6 to 20 carbon atoms which may be halogenated include a phenylene group, a methylphenylene group, a t-butylphenylene group, a fluorophenylene group, a chlorophenylene group, a bromophenylene group and a naphthylene group.
- Examples of the alkanediyl group having 1 to 10 carbon atoms include a methylene group and an ethane-1,2-diyl group.
- Examples of the alkanediyl group having 1 to 10 carbon atoms which may be halogenated include a methylene group, a dimethylmethylene group and a bis (trifluoromethyl) methylene group.
- Examples of the C3-C20 cycloalkanediyl group include a cyclobutanediyl group, a cyclopentanediyl group, and a cyclohexanediyl group.
- Examples of the tetravalent aromatic ring-containing group in Y include a tetravalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, and an anthracene ring, and a formula (g2):> Ar 2 —R 2 —Ar 2 A tetravalent group represented by ⁇ is mentioned.
- Ar 2 is each independently a trivalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, or an anthracene ring, and R 2 is a direct bond or a divalent group. It is.
- the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and an optionally halogenated alkanediyl group.
- Examples of the aromatic hydrocarbon forming Y or Ar 2 include aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene.
- Examples of the alkanediyl group having 1 to 10 carbon atoms which may be halogenated include a methylene group, a dimethylmethylene group and a bis (trifluoromethyl) methylene group.
- the content ratio of the structural unit represented by the formula (1) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.
- the content ratio can be measured by, for example, a nuclear magnetic resonance method.
- resins include JP-A No. 2002-139835, JP-A No. 2004-240144, JP-A No. 2007-056108, JP-A No. 2010-102271, and JP-A No. 2007-192936. Examples thereof include resins described in JP-A No. 2009-237125 and JP-A No. 2012-123378. Details of the method for producing the resin (A) are also described in these documents.
- the weight average molecular weight (Mw) measured by the gel permeation chromatography method of the resin (A) is usually in terms of polystyrene from the viewpoint of the resolution of the photosensitive resin composition, the elastic modulus of the cured film and the crack resistance. Is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 5,000 to 50,000. Details of the method for measuring Mw are as described in the examples.
- the resin (A) is preferably a resin that dissolves 0.001 mg / ml or more in a 2.38% by mass tetramethylammonium hydroxide aqueous solution (23 ° C.).
- the content of the resin (A) is usually 30 to 95% by mass, preferably 40 to 90% by mass, more preferably 50 to 85% by mass with respect to 100% by mass of the solid content of the photosensitive resin composition of the present invention. %.
- Solid content means all the components other than the solvent mentioned later.
- the photosensitive resin composition of the present invention contains a photoacid generator (B).
- the photoacid generator (B) is a compound that generates an acid by a treatment including light irradiation.
- an acid is generated in the exposed portion based on the photoacid generator (B), and the exposed portion is exposed to an alkaline developer based on the action of this acid. Solubility changes.
- the photosensitive resin composition of the present invention may be either a positive type or a negative type.
- the kind of photo-acid generator (B) can be suitably selected according to a positive type or a negative type.
- the photoacid generator (B) include photoacid generators that can be used for positive resists, such as compounds having a quinonediazide group (quinonediazide compounds); onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds And photoacid generators such as sulfonimide compounds and diazomethane compounds that generate strong acids by light irradiation and can be used for negative resists.
- the quinonediazide compound is also referred to as “quinonediazide compound (B1)”, and the other exemplified photoacid generators are also referred to as “other acid generators (B2)”.
- the quinonediazide compound (B1) generates a carboxylic acid by a treatment including light irradiation and development using an alkaline developer.
- the resin film obtained from the composition containing the quinonediazide compound (B1) is a film that is hardly soluble in an alkaline developer. Therefore, a positive pattern can be formed by using the quinonediazide compound (B1).
- the other acid generator (B2) is a compound that generates a strong acid when irradiated with light.
- a cross-linked structure is formed by the acid generated by light irradiation acting on the cross-linking agent (D) described later. Therefore, a negative pattern can be formed by using another acid generator (B2).
- Examples of the quinone diazide compound (B1) include a naphthoquinone diazide compound, and a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid. And an ester compound.
- Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP 2014-186300 A, which are described in the present specification. It shall be.
- quinonediazide compound (B1) examples include, for example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxy.
- a quinonediazide compound (B1) can be used by 1 type, or can be used in combination of 2 or more type.
- the content of the quinonediazide compound (B1) is usually based on 100 parts by mass of the resin (A). The amount is 5 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 15 to 35 parts by mass.
- the content of the quinonediazide compound (B1) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved, and an image faithful to the pattern mask is easily obtained.
- the content of the quinonediazide compound (B1) is less than or equal to the above upper limit value, a resin film excellent in pattern shape is easily obtained and foaming during film formation tends to be prevented.
- the other acid generator (B2) is, for example, at least one selected from an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
- content of an acid generator (B2) is 100 mass parts of resin (A).
- the amount is usually 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass.
- the content of the other acid generator (B2) is equal to or higher than the lower limit, the exposed area is sufficiently cured and the heat resistance is easily improved.
- the content of the other acid generator (B2) is not more than the above upper limit value, a pattern with high resolution is easily obtained without lowering the transparency to exposure light.
- the photosensitive resin composition of the present invention contains a maleimide group-containing compound (C).
- the maleimide group-containing compound (C) is a compound having one or more maleimide groups, preferably two or more, and the upper limit of the number of maleimide groups is preferably 10, more preferably 5.
- the maleimide group is a group that directly acts on the phenolic hydroxyl group at the time of thermal crosslinking or the like. For example, the following reaction is considered to proceed. In this reaction, hydroxyl groups are not newly generated, and phenolic hydroxyl groups are consumed.
- the photosensitive resin composition contains the maleimide group-containing compound (C), for example, a crosslinked structure can be formed in a form in which the phenolic hydroxyl group of the resin (A) is consumed during post-baking.
- a crosslinked structure can be formed in a form in which the phenolic hydroxyl group of the resin (A) is consumed during post-baking.
- chemical resistance can be improved without increasing the crosslinking density so much.
- a compound (C1) having two or more maleimide groups (hereinafter also referred to as “crosslinkable maleimide compound (C1)”) is preferable.
- crosslinkable maleimide compound (C1) For example, a compound represented by the formula (C1) can be given.
- the crosslinkable maleimide compound (C1) By using the crosslinkable maleimide compound (C1), the cured film formed from the photosensitive resin composition can exhibit the effect of improving the chemical resistance.
- R C1 is an organic group, and the organic group is obtained from, for example, an aromatic ring-containing group such as an alkanediyl group or an arylene group, an alicyclic group such as a cycloalkylene group, or an unsaturated fatty acid. Group derived from dimer acid.
- the carbon number of the alkanediyl group is usually 1-20, preferably 2-10.
- the aromatic ring-containing group and alicyclic ring-containing group include a group represented by —A—X—A— in addition to an arylene group having 6 to 20 carbon atoms and a cycloalkylene group having 3 to 20 carbon atoms, —A And a group represented by —O—A—X—A—O—A— and a group represented by —R C2 —A—R C2 —.
- A is a benzene ring or a cyclohexane ring, and may each independently have one or more substituents such as an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
- X is a direct bond, —O—, —SO 2 —, an alkanediyl group having 1 to 10 carbon atoms, or an alicyclic group having 3 to 20 carbon atoms.
- R C2 is an alkanediyl group having 1 to 10 carbon atoms.
- alkanediyl group examples include a methylene group, an ethanediyl group, a propanediyl group, a hexanediyl group, an octanediyl group, a nonanediyl group, and a decanediyl group.
- arylene group examples include a phenylene group, a methylphenylene group, a t-butylphenylene group, and a naphthylene group.
- cycloalkylene group examples include a cyclobutanediyl group, a cyclopentanediyl group, and a cyclohexanediyl group.
- Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
- Examples of the alkoxy group include a methoxy group and an ethoxy group.
- Examples of the alicyclic ring include a cyclohexane ring and a tricyclodecane ring.
- crosslinkable maleimide compound (C1) examples include, for example, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(2,2,4-trimethylhexane) bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-phenylene bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2,6-tolylene bismaleimide, N, N′-p-xylylene bismaleimide, N, N′-m-xylylene bismaleimide, N, N ′-(1,3-dimethylenecyclohexane) bismaleimide, N, N ′-(1,4-dimethylenecyclohexane) bismaleimide, N, N ′-(4,4′-biphenylene) bismaleimide, N, N ′-(4,4′-diphenylmethane) bismaleimide,
- crosslinkable maleimide compound (C1) examples include, for example, bis [4- (4-maleimidophenoxy) phenyl] methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] octane, bis [4- (4-maleimidophenoxy) phenyl] decane, bis [4- (4-maleimidophenoxy) phenyl] cyclohexane, bis [4- (4-maleimidophenoxy) ) Phenyl] -tricyclo- [5.2.1. O 2.6 ] decane.
- At least one hydrogen atom in the benzene ring and the cyclohexane ring in the exemplary compound may be independently substituted with a C 1-10 alkyl group.
- the alkyl group include a methyl group, an ethyl group, and a propyl group.
- a bismaleimide compound in which both ends of polyoxyalkylene diamine are sealed with maleic anhydride can also be used.
- a bismaleimide compound in which both ends of polyoxyethylenediamine are sealed with maleic anhydride a bismaleimide compound in which both ends of polyoxypropylenediamine are sealed with maleic anhydride, and both ends of polyoxybutylenediamine are anhydrous Examples thereof include bismaleimide compounds sealed with maleic acid.
- a compound (C2) having one maleimide group (hereinafter, also referred to as “non-crosslinkable maleimide compound (C2)”) can be used. Even when the non-crosslinkable maleimide compound (C2) is used, for example, the phenolic hydroxyl group of the resin (A) can be consumed at the time of post-baking, and thus the chemical resistance of the obtained film can be improved. Moreover, when using a non-crosslinkable maleimide compound (C2), it is preferable to use a crosslinking agent (D) from a sclerosing
- Non-crosslinkable maleimide compounds (C2) include, for example, N—C 6-20 arylmaleimides such as N-phenylmaleimide and No-methylphenylmaleimide; N-methylmaleimide, N-propylmaleimide, N-butylmaleimide N-C 1-20 alkylmaleimide such as N-decylmaleimide; N-C 3-20 cycloalkylmaleimide such as N-cyclohexylmaleimide.
- a maleimide group containing compound (C) can be used by 1 type, or can be used in combination of 2 or more type.
- the content of the maleimide group-containing compound (C) is usually 0.1 to 200 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin (A). More preferably, it is 5 to 50 parts by mass.
- the content of the maleimide group-containing compound (C) is in the above range, the cured film obtained from the photosensitive resin composition is excellent in both chemical resistance and crack resistance.
- the photosensitive resin composition of the present invention can contain a crosslinking agent (D) as an optional component in order to improve the curability of the resin film and to achieve both chemical resistance and crack resistance of the cured film.
- a crosslinking agent (D) as an optional component in order to improve the curability of the resin film and to achieve both chemical resistance and crack resistance of the cured film.
- the maleimide group-containing compound (C) described above is excluded from the crosslinking agent (D).
- the crosslinking agent (D) acts as a resin (A) or a crosslinking component (curing component) that reacts with the crosslinking agent.
- the crosslinking agent (D) is an epoxy-based crosslinking agent (D1) and a group represented by —CH 2 OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms). It is preferable to include at least one crosslinking agent selected from crosslinking agents (D2) having at least two (which are acyl groups).
- Examples of the epoxy-based crosslinking agent (D1) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, Bisphenol type epoxy resin, biphenyl type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin Naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, Call type epoxy resin, dihydroxynaphthalene type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins.
- the crosslinking agent (D2) has at least two groups represented by —CH 2 OR.
- R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
- Examples of the acyl group include an acetyl group.
- —CH 2 OR it is considered that the methylene group reacts with the aromatic ring of the resin (A) by heat or acid, and the crosslinking reaction proceeds.
- Examples of the crosslinking agent (D2) include compounds having two or more groups represented by the formula (d2-1), compounds having two or more groups represented by the formula (d2-2), and methylol group-containing phenols. Examples thereof include a compound, an alkylmethylol group-containing phenol compound, and an acyloxymethyl group-containing phenol compound.
- m is 1 or 2
- n is 0 or 1
- m + n is 2
- R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An acyl group having 2 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond.
- Examples of the crosslinking agent (D2) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) 2 OH groups) are all alkyl etherified or acyloxylated.
- examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other.
- active methylol groups that are not alkyl etherified or acyloxylated can self-condense within one molecule or condense between two molecules, resulting in the formation of an oligomer component.
- crosslinking agent (D2) examples include the crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297.
- melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetra
- Examples of the methylol group-containing phenol compound, the alkylmethylol group-containing phenol compound, and the acyloxymethyl group-containing phenol compound include compounds represented by the following formulas, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6- Examples include dimethoxymethyl-p-cresol and 2,6-diacetoxymethyl-p-cresol.
- a crosslinking agent (D2) can be used by 1 type, or can be used in combination of 2 or more type.
- a crosslinking agent (D3) other than the epoxy crosslinking agent (D1) and the crosslinking agent (D2) may be used.
- the other crosslinking agent (D3) include an oxetane ring-containing compound, an oxazoline ring-containing compound, an isocyanate group-containing compound (including a blocked one), and an aldehyde group-containing phenol compound.
- the content of the crosslinking agent (D) is usually 1 to 60 parts by weight, preferably 3 to 50 parts by weight, more preferably 100 parts by weight of the resin (A). 5 to 40 parts by mass.
- the content of the crosslinking agent (D) is in the above range, a cured film excellent in both chemical resistance and crack resistance is formed. Further, the curability of the composition is excellent.
- the photosensitive resin composition of the present invention can contain a solvent. By using a solvent, the handleability of the photosensitive resin composition of the present invention can be improved, and the viscosity and storage stability can be adjusted.
- Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether
- Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Recall monopropyl ether acetates, propylene glycol monoalkyl ether acetate such as propylene glycol monobutyl ether acetate; Cellosolves such as
- lactones lactones, lactic acid esters, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers are preferable; ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether are more preferable.
- a solvent can be used by 1 type, or can be used in combination of 2 or more types.
- the content of the solvent in the photosensitive resin composition of the present invention is usually 10 to 95% by mass, preferably 30 to 90% by mass.
- the photosensitive resin composition of the present invention contains various additives such as adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, and alkali solubility promoters. It can contain in the range which does not impair the objective and characteristic of invention.
- the photosensitive resin composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove a foreign material, after mixing each component uniformly, you may filter the obtained mixture with a filter.
- the cured film of the present invention is formed from the above-described photosensitive resin composition.
- a patterned cured film having high chemical resistance and crack resistance and high resolution can be produced.
- the photosensitive resin composition of the present invention can be suitably used for the formation of a cured film and an insulating film.
- a cured film and an insulating film For example, surface protection possessed by electronic components such as circuit boards (semiconductor elements), semiconductor packages, and display elements. It can be suitably used as a material for forming a film, an interlayer insulating film, a planarizing film, etc., or an insulating film material for a high-density mounting substrate.
- This production example includes a step of forming a resin film of the photosensitive resin composition of the present invention on a support (film formation step), a step of exposing the resin film through a desired pattern mask (exposure step), an alkaline property
- the step of forming the desired patterned resin film on the support by developing the resin film with a developer and dissolving and removing the exposed portion in the case of the positive type and the non-exposed portion in the case of the negative type. (Developing step) and a step of heating the patterned resin film (heating step).
- the photosensitive resin composition is coated on a support so that the finally obtained cured film has a thickness of, for example, 0.1 to 100 ⁇ m. This is heated using an oven or a hot plate, for example, at 50 to 140 ° C. for 10 to 360 seconds (pre-baking). In this way, a resin film is formed on the support.
- Examples of the support include a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor chip on the surface of these supports.
- Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
- Exposure process In the exposure process, the resin film is exposed through a desired pattern mask using, for example, a contact aligner, a stepper, or a scanner.
- the exposure light include ultraviolet light and visible light.
- light having a wavelength of 200 to 500 nm eg, i-line (365 nm)
- the irradiation amount of actinic rays varies depending on the type of each component in the photosensitive resin composition, the blending ratio, the thickness of the resin film, etc., but the exposure amount is usually 100 to 5,000 mJ / cm 2 .
- the resin film can be heat-treated after exposure.
- the heat treatment conditions vary depending on the content and film thickness of each component of the photosensitive resin composition, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes.
- development process In the development process, the resin film is developed with an alkaline developer, and the exposed part is dissolved and removed in the case of the positive type and the non-exposed part in the case of the negative type. A desired pattern is formed.
- Examples of the development method include shower development, spray development, immersion development, and paddle development.
- the development conditions are, for example, about 5 to 40 ° C. and about 1 to 10 minutes.
- the alkaline developer examples include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. is dissolved in water so as to have a concentration of 1 to 10% by mass. Is mentioned.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added to the alkaline aqueous solution, for example.
- it after developing the resin film with an alkaline developer, it can be washed with water and dried.
- Heating step is a step that is performed, for example, in order to fully develop characteristics as an insulating film, and the pattern is cured by heating (post-baking).
- the curing conditions are not particularly limited, but for example, heating is performed at a temperature of 100 to 350 ° C. for about 30 minutes to 10 hours depending on the use of the cured film.
- heating can be performed in multiple stages. As described above, a cured film can be obtained.
- an electronic component having the above-described cured film for example, a circuit board (semiconductor) having at least one cured film selected from a surface protective film, an interlayer insulating film, and a planarizing film. Element), a semiconductor package, or an electronic component such as a display element.
- the weight average molecular weight (Mw) of the copolymer (a-1) was 10,000.
- the copolymer (a-1) was a copolymer having 80 mol% of p-hydroxystyrene units and 20 mol% of styrene units.
- Examples 2 to 11 and Comparative Examples 1 to 3 Except for using the components shown in Table 1 below, each component was uniformly mixed with a solvent in the same manner as in Example 1 to prepare photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 3. Predetermined evaluation was performed using the obtained photosensitive resin composition.
- the evaluation method of the evaluation photosensitive resin composition is as follows.
- the resolution photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and then heated at 120 ° C. for 3 minutes using a hot plate to prepare a uniform resin film having a thickness of 7 ⁇ m.
- an aligner manufactured by Suss Microtec, model “MA-150”
- ultraviolet rays from a high-pressure mercury lamp were irradiated to the resin film through a pattern mask at an exposure dose of 800 mJ / cm 2 at a wavelength of 350 nm.
- the resin film was subjected to immersion development for 240 seconds at 23 ° C. using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass.
- the developed resin film was washed with ultrapure water for 60 seconds, air-dried with air, then observed with an optical microscope, and the resolution of the minimum pattern size resolved was defined as the resolution.
- the chemical-resistant photosensitive resin composition was applied to a 4-inch silicon wafer and heated at 120 ° C. for 3 minutes using a hot plate to prepare a resin film having a thickness of 10 ⁇ m. Thereafter, in a convection oven at 120 ° C. for 30 minutes, at 150 ° C. for 30 minutes, and in Examples 1, 2 and Comparative Example 1 at 250 ° C. for 1 hour, Examples 3 to 11 and Comparative Examples 2 and 3 Then, it heated at 200 degreeC for 1 hour, and obtained the cured film.
- a flux product name “WF-6317”, manufactured by Senju Metal Co., Ltd.
- the crack resistance was evaluated by measuring the storage elastic modulus (E ′).
- a photosensitive resin composition was applied onto a substrate with a release material, and heated at 120 ° C. for 5 minutes using a hot plate to form a uniform resin film having a thickness of 15 ⁇ m.
- the resin film was subjected to convection oven at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and in Examples 1 and 2 and Comparative Example 1, 250 ° C. for 1 hour. 11 and Comparative Examples 2 and 3 were heated at 200 ° C. for 1 hour to form a cured film.
- the cured film was peeled off from the substrate with the release material, and the cured film was cut into a 2.5 cm ⁇ 0.3 cm strip shape.
- the storage elastic modulus (E ′) of the strip-like cured film was measured with a TMA device (device name “TMA / SS6100”, manufactured by SII Nanotechnology Co., Ltd.). The measurement conditions are as follows. Chuck distance: 2cm Measurement frequency: 0.1 Hz Measurement temperature range: 23-330 ° C, temperature rising speed: 5 ° C / min
- the cured film obtained from the photosensitive resin composition containing the maleimide group-containing compound (C) is equivalent in chemical resistance to the cured film obtained from the photosensitive resin composition not containing the maleimide group-containing compound (C).
- the storage elastic modulus (E ′ in the high temperature region above the curing temperature (Examples 1 and 2 and Comparative Example 1 is 250 ° C. or higher, Examples 3 to 11 and Comparative Examples 2 and 3 are 200 ° C. or higher). ) Is low, that is, since the crosslink density is low, it is judged to be excellent in crack resistance.
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Abstract
[Problem] To simultaneously achieve chemical resistance and crack resistance in a cured film obtained from a photosensitive resin composition comprising a phenolic hydroxyl-containing resin as an alkali-soluble resin. [Solution] This photosensitive resin composition comprises a phenolic hydroxyl-containing resin (A), a photoacid generating agent (B), and a maleimide group-containing compound (C).
Description
本発明は、電子部品等が有する表面保護膜および層間絶縁膜等の形成に好適に用いられる感光性樹脂組成物に関し、さらに、前記組成物から形成される硬化膜およびその製造方法、ならびに前記硬化膜を有する電子部品に関する。
The present invention relates to a photosensitive resin composition suitably used for forming a surface protective film, an interlayer insulating film, and the like of an electronic component, and further, a cured film formed from the composition, a method for producing the same, and the curing The present invention relates to an electronic component having a film.
従来、電子部品中の半導体素子に用いられる表面保護膜および層間絶縁膜等を形成する際に使用される材料として、様々な感光性樹脂組成物が提案されている。例えば、アルカリ可溶性樹脂としてフェノール性水酸基を有する樹脂を含有する感光性樹脂組成物が検討されている(特許文献1および2)。
Conventionally, various photosensitive resin compositions have been proposed as materials used when forming a surface protective film, an interlayer insulating film, and the like used for semiconductor elements in electronic components. For example, a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin has been studied (Patent Documents 1 and 2).
アルカリ可溶性樹脂としてフェノール性水酸基を有する樹脂を含有する感光性樹脂組成物には、感光性樹脂組成物から得られる硬化膜の、薬品耐性とクラック耐性との両立が難しいという課題があり、これは以下の理由によると推定される。フェノール性水酸基を有する樹脂の架橋に、例えばエポキシ系架橋剤のみを用いると、架橋反応においてエポキシ環の開環による水酸基が発生し、またメチロール系架橋剤のみを用いると、架橋反応後にもフェノール性水酸基が残存するため、薬品耐性が悪くなる。一方、薬品耐性を上げるために、エポキシ系架橋剤またはメチロール系架橋剤を用いて硬化膜の架橋密度を上げると、硬化膜の伸び物性が低下し、クラック耐性が悪くなる。
A photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin has a problem that it is difficult to achieve both chemical resistance and crack resistance of a cured film obtained from the photosensitive resin composition. It is estimated that the reason is as follows. For example, if only an epoxy-based crosslinking agent is used to crosslink a resin having a phenolic hydroxyl group, a hydroxyl group is generated due to the opening of an epoxy ring in the crosslinking reaction. If only a methylol-based crosslinking agent is used, a phenolic compound is generated even after the crosslinking reaction. Since the hydroxyl group remains, chemical resistance deteriorates. On the other hand, when the crosslink density of the cured film is increased using an epoxy-based cross-linking agent or a methylol-based cross-linking agent in order to increase chemical resistance, the stretched physical properties of the cured film are lowered and crack resistance is deteriorated.
本発明者らは上記課題を解決するため鋭意検討を行った。その結果、フェノール性水酸基を有する樹脂を含む下記組成の感光性樹脂組成物が上記課題を解決できることを見出し、本発明を完成するに至った。
The present inventors have intensively studied to solve the above problems. As a result, it has been found that a photosensitive resin composition having the following composition containing a resin having a phenolic hydroxyl group can solve the above problems, and has completed the present invention.
本発明は、例えば以下の[1]~[8]である。
[1]フェノール性水酸基を有する樹脂(A)と、光酸発生剤(B)と、マレイミド基含有化合物(C)とを含有する感光性樹脂組成物。 The present invention includes, for example, the following [1] to [8].
[1] A photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C).
[1]フェノール性水酸基を有する樹脂(A)と、光酸発生剤(B)と、マレイミド基含有化合物(C)とを含有する感光性樹脂組成物。 The present invention includes, for example, the following [1] to [8].
[1] A photosensitive resin composition containing a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C).
[2]前記マレイミド基含有化合物(C)が、マレイミド基を2つ以上有する化合物(C1)を含む前記[1]に記載の感光性樹脂組成物。
[2] The photosensitive resin composition according to [1], wherein the maleimide group-containing compound (C) includes a compound (C1) having two or more maleimide groups.
[3]さらに、架橋剤(D)(だだし、マレイミド基含有化合物(C)を除く)を含有する、前記[1]または[2]に記載の感光性樹脂組成物。
[3] The photosensitive resin composition according to the above [1] or [2], further comprising a crosslinking agent (D) (but excluding the maleimide group-containing compound (C)).
[4]前記架橋剤(D)が、エポキシ系架橋剤(D1)、および-CH2ORで表される基(前記式中、Rは、水素原子、炭素数1~10のアルキル基または炭素数2~10のアシル基である)を少なくとも2つ有する架橋剤(D2)から選ばれる少なくとも1種の架橋剤を含む前記[3]に記載の感光性樹脂組成物。
[4] The crosslinking agent (D) is an epoxy crosslinking agent (D1) and a group represented by —CH 2 OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or carbon The photosensitive resin composition according to the above [3], comprising at least one crosslinking agent selected from crosslinking agents (D2) having at least two (which are acyl groups of 2 to 10).
[5]前記光酸発生剤(B)が、キノンジアジド化合物(B1)を含む、前記[1]~[4]のいずれか1項に記載の感光性樹脂組成物。
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photoacid generator (B) includes a quinonediazide compound (B1).
[6]前記[1]~[5]のいずれか1項に記載の感光性樹脂組成物の樹脂膜を支持体上に形成する工程、前記樹脂膜を露光する工程、アルカリ性現像液により前記樹脂膜を現像してパターン化樹脂膜を形成する工程、および前記パターン化樹脂膜を加熱する工程を有する硬化膜の製造方法。
[6] A step of forming a resin film of the photosensitive resin composition as described in any one of [1] to [5] on a support, a step of exposing the resin film, and the resin with an alkaline developer. The manufacturing method of the cured film which has the process of developing a film | membrane and forming a patterned resin film, and the process of heating the said patterned resin film.
[7]前記[1]~[5]のいずれか1項に記載の感光性樹脂組成物から形成される硬化膜。
[7] A cured film formed from the photosensitive resin composition according to any one of [1] to [5].
[8]前記[7]の硬化膜を有する電子部品。
[8] An electronic component having the cured film of [7].
本発明によれば、アルカリ可溶性樹脂としてフェノール性水酸基を有する樹脂を含有する感光性樹脂組成物から得られる硬化膜の、薬品耐性とクラック耐性とを両立することができる。
According to the present invention, both chemical resistance and crack resistance of a cured film obtained from a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin can be achieved.
以下、本発明を実施するための形態について好適態様も含めて説明する。
〔感光性樹脂組成物〕
本発明の感光性樹脂組成物は、以下に説明する、フェノール性水酸基を有する樹脂(A)と、光酸発生剤(B)と、マレイミド基含有化合物(C)とを含有する。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described including preferred embodiments.
[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C) described below.
〔感光性樹脂組成物〕
本発明の感光性樹脂組成物は、以下に説明する、フェノール性水酸基を有する樹脂(A)と、光酸発生剤(B)と、マレイミド基含有化合物(C)とを含有する。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described including preferred embodiments.
[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C) described below.
〈樹脂(A)〉
フェノール性水酸基を有する樹脂(A)としては、例えば、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位を有する重合体(a1)(以下、「重合体(a1)」ともいう)、ノボラック樹脂(a2)、ポリベンゾオキサゾール前駆体(a3)、フェノール性水酸基を有するポリイミド、フェノール-キシリレングリコール縮合樹脂、クレゾール-キシリレングリコール縮合樹脂、フェノール-ジシクロペンタジエン縮合樹脂が挙げられる。これらの中でも、組成物の硬化性の観点から、重合体(a1)、ノボラック樹脂(a2)およびポリベンゾオキサゾール前駆体(a3)が好ましく、重合体(a1)がより好ましい。
樹脂(A)は1種で用いることができ、または2種以上を併用して用いることができる。 <Resin (A)>
Examples of the resin (A) having a phenolic hydroxyl group include a polymer (a1) having a structural unit derived from a radical polymerizable monomer having a phenolic hydroxyl group (hereinafter also referred to as “polymer (a1)”), a novolac resin. (A2), polybenzoxazole precursor (a3), polyimide having a phenolic hydroxyl group, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin. Among these, from the viewpoint of curability of the composition, the polymer (a1), the novolak resin (a2), and the polybenzoxazole precursor (a3) are preferable, and the polymer (a1) is more preferable.
Resin (A) can be used by 1 type, or can be used in combination of 2 or more type.
フェノール性水酸基を有する樹脂(A)としては、例えば、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位を有する重合体(a1)(以下、「重合体(a1)」ともいう)、ノボラック樹脂(a2)、ポリベンゾオキサゾール前駆体(a3)、フェノール性水酸基を有するポリイミド、フェノール-キシリレングリコール縮合樹脂、クレゾール-キシリレングリコール縮合樹脂、フェノール-ジシクロペンタジエン縮合樹脂が挙げられる。これらの中でも、組成物の硬化性の観点から、重合体(a1)、ノボラック樹脂(a2)およびポリベンゾオキサゾール前駆体(a3)が好ましく、重合体(a1)がより好ましい。
樹脂(A)は1種で用いることができ、または2種以上を併用して用いることができる。 <Resin (A)>
Examples of the resin (A) having a phenolic hydroxyl group include a polymer (a1) having a structural unit derived from a radical polymerizable monomer having a phenolic hydroxyl group (hereinafter also referred to as “polymer (a1)”), a novolac resin. (A2), polybenzoxazole precursor (a3), polyimide having a phenolic hydroxyl group, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin. Among these, from the viewpoint of curability of the composition, the polymer (a1), the novolak resin (a2), and the polybenzoxazole precursor (a3) are preferable, and the polymer (a1) is more preferable.
Resin (A) can be used by 1 type, or can be used in combination of 2 or more type.
《重合体(a1)》
重合体(a1)としては、例えば、フェノール性水酸基を有するラジカル重合性モノマーの単独または共重合体、フェノール性水酸基を有するラジカル重合性モノマーとその他のラジカル重合性モノマーとの共重合体が挙げられる。 << Polymer (a1) >>
Examples of the polymer (a1) include a radical polymerizable monomer having a phenolic hydroxyl group alone or a copolymer, and a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer. .
重合体(a1)としては、例えば、フェノール性水酸基を有するラジカル重合性モノマーの単独または共重合体、フェノール性水酸基を有するラジカル重合性モノマーとその他のラジカル重合性モノマーとの共重合体が挙げられる。 << Polymer (a1) >>
Examples of the polymer (a1) include a radical polymerizable monomer having a phenolic hydroxyl group alone or a copolymer, and a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer. .
フェノール性水酸基を有するラジカル重合性モノマーとしては、例えば、o-ヒドロキシスチレン、m-ヒドロキシスチレン、p-ヒドロキシスチレン、o-イソプロペニルフェノール、m-イソプロペニルフェノール、p-イソプロペニルフェノール等のヒドロキシスチレン系モノマー;ヒドロキシスチレン系モノマーの芳香環炭素に結合した1または2以上の水素原子をアルキル、アルコキシル、ハロゲン、ハロアルキル、ニトロまたはシアノに置換してなるモノマー;ビニルヒドロキノン、5-ビニルピロガロール、6-ビニルピロガロールが挙げられる。また、前記モノマーのフェノール性水酸基をアルキル基やシリル基等で保護してなるモノマーを挙げることもできる。前記のフェノール性水酸基を保護してなるモノマーを用いる場合、重合体を形成後、当該保護を外すことでフェノール性水酸基を有する重合体(a1)とすることができる。前記モノマーは1種で用いることができ、または2種以上を併用して用いることができる。
Examples of the radical polymerizable monomer having a phenolic hydroxyl group include hydroxystyrene such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol. Monomers: Monomers formed by substituting one or more hydrogen atoms bonded to the aromatic ring carbon of hydroxystyrene monomers with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano; vinyl hydroquinone, 5-vinyl pyrogallol, 6- Vinyl pyrogallol is mentioned. Moreover, the monomer which protects the phenolic hydroxyl group of the said monomer with an alkyl group, a silyl group, etc. can also be mentioned. When using the monomer which protects the said phenolic hydroxyl group, it can be set as the polymer (a1) which has a phenolic hydroxyl group by removing the said protection after forming a polymer. The said monomer can be used by 1 type, or can be used in combination of 2 or more type.
その他のラジカル重合性モノマーとしては、例えば、スチレン、α-メチルスチレン、o-ビニルベンジルグリシジルエーテル、m-ビニルベンジルグリシジルエーテル、p-ビニルベンジルグリシジルエーテル等のスチレン系モノマー;スチレン系モノマーの芳香環炭素に結合した1または2以上の水素原子をアルキル、アルコキシル、ハロゲン、ハロアルキル、ニトロまたはシアノに置換してなるモノマー;ブタジエン、イソプレン、クロロプレン等のジエン;不飽和モノカルボン酸、不飽和ジカルボン酸およびそのハーフエステル等の不飽和カルボン酸;o-ビニル安息香酸、m-ビニル安息香酸、p-ビニル安息香酸またはこれらのモノマーの芳香環炭素に結合した1もしくは2以上の水素原子をアルキル、アルコキシル、ハロゲン、ハロアルキル、ニトロもしくはシアノに置換してなるモノマー;(メタ)アクリル酸グリシジル等の(メタ)アクリル酸エステル、(メタ)アクリロニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、弗化ビニル、弗化ビニリデン、N-ビニルピロリドン、ビニルピリジン、酢酸ビニル、N-フェニルマレイミド、N-シクロヘキシルマレイミド、N-(メタ)アクリロイルフタルイミド、(3,4-エポキシシクロヘキシル)メチル(メタ)アクリレートが挙げられる。前記モノマーは1種で用いることができ、または2種以上を併用して用いることができる。
Examples of other radical polymerizable monomers include styrene monomers such as styrene, α-methyl styrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; aromatic rings of styrene monomers Monomers formed by substituting one or more hydrogen atoms bonded to carbon with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano; dienes such as butadiene, isoprene, chloroprene; unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and An unsaturated carboxylic acid such as a half ester; o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, or one or more hydrogen atoms bonded to the aromatic ring carbon of these monomers, alkyl, alkoxyl, Haloge Monomers substituted with haloalkyl, nitro or cyano; (meth) acrylic esters such as glycidyl (meth) acrylate, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N -Vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, (3,4-epoxycyclohexyl) methyl (meth) acrylate. The said monomer can be used by 1 type, or can be used in combination of 2 or more type.
上記ラジカル重合性モノマーの重合体において、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位の含有割合は、フェノール性水酸基を有するラジカル重合性モノマー由来の構造単位とその他のラジカル重合性モノマー由来の構造単位との含有割合の合計100モル%に対して、好ましくは30モル%以上、より好ましくは40~95モル%である。
In the polymer of the radical polymerizable monomer, the content ratio of the structural unit derived from the radical polymerizable monomer having a phenolic hydroxyl group is derived from the structural unit derived from the radical polymerizable monomer having a phenolic hydroxyl group and the other radical polymerizable monomer. It is preferably 30 mol% or more, more preferably 40 to 95 mol%, with respect to a total content of 100 mol% with the structural unit.
上記ラジカル重合性モノマーの重合体としては、好ましくは、ポリp-ヒドロキシスチレン、m-ヒドロキシスチレン/p-ヒドロキシスチレン共重合体、p-ヒドロキシスチレン/スチレン共重合体、p-ヒドロキシスチレン/p-ビニルベンジルグリシジルエーテル/スチレン共重合体、p-ヒドロキシスチレン/(3,4-エポキシシクロヘキシル)メチルメタクリレート共重合体、p-ヒドロキシスチレン/(3,4-エポキシシクロヘキシル)メチルメタクリレート/スチレン共重合体等のヒドロキシスチレン系重合体が挙げられる。
As the polymer of the radical polymerizable monomer, poly-p-hydroxystyrene, m-hydroxystyrene / p-hydroxystyrene copolymer, p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / p- Vinyl benzyl glycidyl ether / styrene copolymer, p-hydroxystyrene / (3,4-epoxycyclohexyl) methyl methacrylate copolymer, p-hydroxystyrene / (3,4-epoxycyclohexyl) methyl methacrylate / styrene copolymer, etc. The hydroxy styrene-type polymer of this is mentioned.
《ノボラック樹脂(a2)》
ノボラック樹脂(a2)は、例えば、フェノール類とアルデヒド類とを酸触媒の存在下で縮合させることにより得ることができる。フェノール類としては、例えば、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、o-エチルフェノール、m-エチルフェノール、p-エチルフェノール、o-ブチルフェノール、m-ブチルフェノール、p-ブチルフェノール、2,3-キシレノール、2,4-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール、2,3,5-トリメチルフェノール、3,4,5-トリメチルフェノール、カテコール、レゾルシノール、ピロガロール、α-ナフトール、β-ナフトールが挙げられる。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、サリチルアルデヒドが挙げられる。 << Novolac resin (a2) >>
The novolac resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Examples thereof include phenol, catechol, resorcinol, pyrogallol, α-naphthol, and β-naphthol. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde.
ノボラック樹脂(a2)は、例えば、フェノール類とアルデヒド類とを酸触媒の存在下で縮合させることにより得ることができる。フェノール類としては、例えば、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、o-エチルフェノール、m-エチルフェノール、p-エチルフェノール、o-ブチルフェノール、m-ブチルフェノール、p-ブチルフェノール、2,3-キシレノール、2,4-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール、2,3,5-トリメチルフェノール、3,4,5-トリメチルフェノール、カテコール、レゾルシノール、ピロガロール、α-ナフトール、β-ナフトールが挙げられる。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、サリチルアルデヒドが挙げられる。 << Novolac resin (a2) >>
The novolac resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Examples thereof include phenol, catechol, resorcinol, pyrogallol, α-naphthol, and β-naphthol. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde.
ノボラック樹脂(a2)の具体例としては、フェノール/ホルムアルデヒド縮合ノボラック樹脂、クレゾール/ホルムアルデヒド縮合ノボラック樹脂、クレゾール/サリチルアルデヒド縮合ノボラック樹脂、フェノール-ナフトール/ホルムアルデヒド縮合ノボラック樹脂、ノボラック樹脂をブタジエン系重合体などの重合性ビニル基を有するゴム状ポリマーで変性してなる樹脂(例えば、特開2010-015101号公報に記載の樹脂)が挙げられる。
Specific examples of the novolak resin (a2) include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, a cresol / salicylaldehyde condensed novolak resin, a phenol-naphthol / formaldehyde condensed novolak resin, a novolac resin, and the like. And a resin modified with a rubber-like polymer having a polymerizable vinyl group (for example, a resin described in JP 2010-015101 A).
《ポリベンゾオキサゾール前駆体(a3)》
ポリベンゾオキサゾール前駆体(a3)としては、例えば、式(1)に示す構造単位を有する重合体が挙げられる。ポリベンゾオキサゾール前駆体(a3)は、1種の構造単位を有する重合体でも、2種以上の構造単位を有する重合体でもよい。 << Polybenzoxazole precursor (a3) >>
As a polybenzoxazole precursor (a3), the polymer which has a structural unit shown to Formula (1) is mentioned, for example. The polybenzoxazole precursor (a3) may be a polymer having one type of structural unit or a polymer having two or more types of structural units.
ポリベンゾオキサゾール前駆体(a3)としては、例えば、式(1)に示す構造単位を有する重合体が挙げられる。ポリベンゾオキサゾール前駆体(a3)は、1種の構造単位を有する重合体でも、2種以上の構造単位を有する重合体でもよい。 << Polybenzoxazole precursor (a3) >>
As a polybenzoxazole precursor (a3), the polymer which has a structural unit shown to Formula (1) is mentioned, for example. The polybenzoxazole precursor (a3) may be a polymer having one type of structural unit or a polymer having two or more types of structural units.
Xにおける2価の有機基としては、例えば、ハロゲン化されていてもよい炭素数6~20のアリーレン基、式(g1):-Ar1-R1-Ar1-で表される2価の基、炭素数1~10のアルカンジイル基、および炭素数3~20のシクロアルカンジイル基が挙げられる。式(g1)中、Ar1は、それぞれ独立に、ハロゲン化されていてもよい炭素数6~20のアリーレン基であり、R1は、直接結合または2価の基である。2価の基としては、例えば、酸素原子、硫黄原子、スルホニル基、カルボニル基、ハロゲン化されていてもよい炭素数1~10のアルカンジイル基が挙げられる。
The divalent organic group represented by X, for example, halogenated carbon atoms and optionally 6-20 arylene group, the formula (g1): - Ar 1 -R 1 -Ar 1 - a divalent represented Groups, alkanediyl groups having 1 to 10 carbon atoms, and cycloalkanediyl groups having 3 to 20 carbon atoms. In formula (g1), Ar 1 is each independently an arylene group having 6 to 20 carbon atoms which may be halogenated, and R 1 is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and an optionally halogenated alkanediyl group.
ハロゲン化されていてもよい炭素数6~20のアリーレン基としては、例えば、フェニレン基、メチルフェニレン基、t-ブチルフェニレン基、フルオロフェニレン基、クロロフェニレン基、ブロモフェニレン基、ナフチレン基が挙げられる。炭素数1~10のアルカンジイル基としては、例えば、メチレン基、エタン-1,2-ジイル基が挙げられる。ハロゲン化されていてもよい炭素数1~10のアルカンジイル基としては、例えば、メチレン基、ジメチルメチレン基、ビス(トリフルオロメチル)メチレン基が挙げられる。炭素数3~20のシクロアルカンジイル基としては、例えば、シクロブタンジイル基、シクロペンタンジイル基、シクロヘキサンジイル基が挙げられる。
Examples of the arylene group having 6 to 20 carbon atoms which may be halogenated include a phenylene group, a methylphenylene group, a t-butylphenylene group, a fluorophenylene group, a chlorophenylene group, a bromophenylene group and a naphthylene group. . Examples of the alkanediyl group having 1 to 10 carbon atoms include a methylene group and an ethane-1,2-diyl group. Examples of the alkanediyl group having 1 to 10 carbon atoms which may be halogenated include a methylene group, a dimethylmethylene group and a bis (trifluoromethyl) methylene group. Examples of the C3-C20 cycloalkanediyl group include a cyclobutanediyl group, a cyclopentanediyl group, and a cyclohexanediyl group.
Yにおける4価の芳香環含有基としては、例えば、ベンゼン環、ナフタレン環、アントラセン環等の、芳香族炭化水素に由来する4価の基、式(g2):>Ar2-R2-Ar2<で表される4価の基が挙げられる。
Examples of the tetravalent aromatic ring-containing group in Y include a tetravalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, and an anthracene ring, and a formula (g2):> Ar 2 —R 2 —Ar 2 A tetravalent group represented by <is mentioned.
式(g2)中、Ar2は、それぞれ独立に、ベンゼン環、ナフタレン環、アントラセン環等の、芳香族炭化水素に由来する3価の基であり、R2は、直接結合または2価の基である。2価の基としては、例えば、酸素原子、硫黄原子、スルホニル基、カルボニル基、ハロゲン化されていてもよい炭素数1~10のアルカンジイル基が挙げられる。
In the formula (g2), Ar 2 is each independently a trivalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, or an anthracene ring, and R 2 is a direct bond or a divalent group. It is. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and an optionally halogenated alkanediyl group.
YまたはAr2を形成する芳香族炭化水素としては、例えば、ベンゼン、ナフタレン、アントラセン等の、炭素数6~20の芳香族炭化水素が挙げられる。ハロゲン化されていてもよい炭素数1~10のアルカンジイル基としては、例えば、メチレン基、ジメチルメチレン基、ビス(トリフルオロメチル)メチレン基が挙げられる。
Examples of the aromatic hydrocarbon forming Y or Ar 2 include aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene. Examples of the alkanediyl group having 1 to 10 carbon atoms which may be halogenated include a methylene group, a dimethylmethylene group and a bis (trifluoromethyl) methylene group.
ポリベンゾオキサゾール前駆体(a3)において、式(1)に示す構造単位の含有割合は、通常は70質量%以上、好ましくは80質量%以上、より好ましくは90質量%以上である。前記含有割合は、例えば、核磁気共鳴法により測定することができる。
In the polybenzoxazole precursor (a3), the content ratio of the structural unit represented by the formula (1) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The content ratio can be measured by, for example, a nuclear magnetic resonance method.
《その他の樹脂》
樹脂(A)のその他の具体例としては、特開2002-139835号公報、特開2004-240144号公報、特開2007-056108号公報、特開2010-102271号公報、特開2007-192936号公報、特開2009-237125号公報および特開2012-123378号公報に記載された樹脂が挙げられる。樹脂(A)の製造方法の詳細も、これらの文献に記載されている。 《Other resins》
Other specific examples of the resin (A) include JP-A No. 2002-139835, JP-A No. 2004-240144, JP-A No. 2007-056108, JP-A No. 2010-102271, and JP-A No. 2007-192936. Examples thereof include resins described in JP-A No. 2009-237125 and JP-A No. 2012-123378. Details of the method for producing the resin (A) are also described in these documents.
樹脂(A)のその他の具体例としては、特開2002-139835号公報、特開2004-240144号公報、特開2007-056108号公報、特開2010-102271号公報、特開2007-192936号公報、特開2009-237125号公報および特開2012-123378号公報に記載された樹脂が挙げられる。樹脂(A)の製造方法の詳細も、これらの文献に記載されている。 《Other resins》
Other specific examples of the resin (A) include JP-A No. 2002-139835, JP-A No. 2004-240144, JP-A No. 2007-056108, JP-A No. 2010-102271, and JP-A No. 2007-192936. Examples thereof include resins described in JP-A No. 2009-237125 and JP-A No. 2012-123378. Details of the method for producing the resin (A) are also described in these documents.
《樹脂(A)の構成》
樹脂(A)のゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量(Mw)は、感光性樹脂組成物の解像性、硬化膜の弾性率およびクラック耐性の観点から、ポリスチレン換算で、通常は1,000~200,000、好ましくは2,000~100,000、さらに好ましくは5,000~50,000である。Mwの測定方法の詳細は、実施例に記載したとおりである。 << Configuration of Resin (A) >>
The weight average molecular weight (Mw) measured by the gel permeation chromatography method of the resin (A) is usually in terms of polystyrene from the viewpoint of the resolution of the photosensitive resin composition, the elastic modulus of the cured film and the crack resistance. Is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 5,000 to 50,000. Details of the method for measuring Mw are as described in the examples.
樹脂(A)のゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量(Mw)は、感光性樹脂組成物の解像性、硬化膜の弾性率およびクラック耐性の観点から、ポリスチレン換算で、通常は1,000~200,000、好ましくは2,000~100,000、さらに好ましくは5,000~50,000である。Mwの測定方法の詳細は、実施例に記載したとおりである。 << Configuration of Resin (A) >>
The weight average molecular weight (Mw) measured by the gel permeation chromatography method of the resin (A) is usually in terms of polystyrene from the viewpoint of the resolution of the photosensitive resin composition, the elastic modulus of the cured film and the crack resistance. Is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 5,000 to 50,000. Details of the method for measuring Mw are as described in the examples.
樹脂(A)は、2.38質量%濃度のテトラメチルアンモニウムハイドロキサイド水溶液(23℃)に、0.001mg/ml以上溶解する樹脂であることが好ましい。
樹脂(A)の含有割合は、本発明の感光性樹脂組成物の固形分100質量%に対して、通常は30~95質量%、好ましくは40~90質量%、さらに好ましくは50~85質量%である。樹脂(A)の含有割合が前記範囲にあると、解像度に優れた硬化膜を形成可能な感光性樹脂組成物が得られる傾向にある。固形分は、後述する溶剤以外の全成分をいう。 The resin (A) is preferably a resin that dissolves 0.001 mg / ml or more in a 2.38% by mass tetramethylammonium hydroxide aqueous solution (23 ° C.).
The content of the resin (A) is usually 30 to 95% by mass, preferably 40 to 90% by mass, more preferably 50 to 85% by mass with respect to 100% by mass of the solid content of the photosensitive resin composition of the present invention. %. When the content ratio of the resin (A) is in the above range, a photosensitive resin composition capable of forming a cured film excellent in resolution tends to be obtained. Solid content means all the components other than the solvent mentioned later.
樹脂(A)の含有割合は、本発明の感光性樹脂組成物の固形分100質量%に対して、通常は30~95質量%、好ましくは40~90質量%、さらに好ましくは50~85質量%である。樹脂(A)の含有割合が前記範囲にあると、解像度に優れた硬化膜を形成可能な感光性樹脂組成物が得られる傾向にある。固形分は、後述する溶剤以外の全成分をいう。 The resin (A) is preferably a resin that dissolves 0.001 mg / ml or more in a 2.38% by mass tetramethylammonium hydroxide aqueous solution (23 ° C.).
The content of the resin (A) is usually 30 to 95% by mass, preferably 40 to 90% by mass, more preferably 50 to 85% by mass with respect to 100% by mass of the solid content of the photosensitive resin composition of the present invention. %. When the content ratio of the resin (A) is in the above range, a photosensitive resin composition capable of forming a cured film excellent in resolution tends to be obtained. Solid content means all the components other than the solvent mentioned later.
〈光酸発生剤(B)〉
本発明の感光性樹脂組成物は、光酸発生剤(B)を含有する。
光酸発生剤(B)は、光照射を含む処理によって酸を発生する化合物である。本発明の感光性樹脂組成物から形成される樹脂膜に対する露光処理によって、光酸発生剤(B)に基づき露光部に酸が発生し、この酸の作用に基づき露光部のアルカリ性現像液への溶解性が変化する。 <Photoacid generator (B)>
The photosensitive resin composition of the present invention contains a photoacid generator (B).
The photoacid generator (B) is a compound that generates an acid by a treatment including light irradiation. By the exposure treatment on the resin film formed from the photosensitive resin composition of the present invention, an acid is generated in the exposed portion based on the photoacid generator (B), and the exposed portion is exposed to an alkaline developer based on the action of this acid. Solubility changes.
本発明の感光性樹脂組成物は、光酸発生剤(B)を含有する。
光酸発生剤(B)は、光照射を含む処理によって酸を発生する化合物である。本発明の感光性樹脂組成物から形成される樹脂膜に対する露光処理によって、光酸発生剤(B)に基づき露光部に酸が発生し、この酸の作用に基づき露光部のアルカリ性現像液への溶解性が変化する。 <Photoacid generator (B)>
The photosensitive resin composition of the present invention contains a photoacid generator (B).
The photoacid generator (B) is a compound that generates an acid by a treatment including light irradiation. By the exposure treatment on the resin film formed from the photosensitive resin composition of the present invention, an acid is generated in the exposed portion based on the photoacid generator (B), and the exposed portion is exposed to an alkaline developer based on the action of this acid. Solubility changes.
本発明の感光性樹脂組成物は、ポジ型またはネガ型のいずれであってもよい。光酸発生剤(B)の種類は、ポジ型またはネガ型に応じて、適宜選択することができる。
光酸発生剤(B)としては、例えば、キノンジアジド基を有する化合物(キノンジアジド化合物)等の、ポジ型レジストに使用しうる光酸発生剤;オニウム塩化合物、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物、ジアゾメタン化合物等の、光照射により強酸を発生し、ネガ型レジストに使用しうる光酸発生剤が挙げられる。以下、キノンジアジド化合物を「キノンジアジド化合物(B1)」ともいい、これ以外の前記例示の光酸発生剤を「他の酸発生剤(B2)」ともいう。 The photosensitive resin composition of the present invention may be either a positive type or a negative type. The kind of photo-acid generator (B) can be suitably selected according to a positive type or a negative type.
Examples of the photoacid generator (B) include photoacid generators that can be used for positive resists, such as compounds having a quinonediazide group (quinonediazide compounds); onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds And photoacid generators such as sulfonimide compounds and diazomethane compounds that generate strong acids by light irradiation and can be used for negative resists. Hereinafter, the quinonediazide compound is also referred to as “quinonediazide compound (B1)”, and the other exemplified photoacid generators are also referred to as “other acid generators (B2)”.
光酸発生剤(B)としては、例えば、キノンジアジド基を有する化合物(キノンジアジド化合物)等の、ポジ型レジストに使用しうる光酸発生剤;オニウム塩化合物、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物、ジアゾメタン化合物等の、光照射により強酸を発生し、ネガ型レジストに使用しうる光酸発生剤が挙げられる。以下、キノンジアジド化合物を「キノンジアジド化合物(B1)」ともいい、これ以外の前記例示の光酸発生剤を「他の酸発生剤(B2)」ともいう。 The photosensitive resin composition of the present invention may be either a positive type or a negative type. The kind of photo-acid generator (B) can be suitably selected according to a positive type or a negative type.
Examples of the photoacid generator (B) include photoacid generators that can be used for positive resists, such as compounds having a quinonediazide group (quinonediazide compounds); onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds And photoacid generators such as sulfonimide compounds and diazomethane compounds that generate strong acids by light irradiation and can be used for negative resists. Hereinafter, the quinonediazide compound is also referred to as “quinonediazide compound (B1)”, and the other exemplified photoacid generators are also referred to as “other acid generators (B2)”.
キノンジアジド化合物(B1)は、光照射およびアルカリ性現像液を用いた現像を含む処理によってカルボン酸を発生する。キノンジアジド化合物(B1)を含有する組成物から得られる樹脂膜は、アルカリ性現像液に対して難溶な膜である。したがって、キノンジアジド化合物(B1)を用いることで、ポジ型のパターンを形成することができる。
The quinonediazide compound (B1) generates a carboxylic acid by a treatment including light irradiation and development using an alkaline developer. The resin film obtained from the composition containing the quinonediazide compound (B1) is a film that is hardly soluble in an alkaline developer. Therefore, a positive pattern can be formed by using the quinonediazide compound (B1).
他の酸発生剤(B2)は、光照射により強酸を発生する化合物である。他の酸発生剤(B2)を含有する組成物から得られる樹脂膜は、光照射により発生する前記酸が後述する架橋剤(D)等に作用することにより架橋構造が形成される。したがって、他の酸発生剤(B2)を用いることで、ネガ型のパターンを形成することができる。
The other acid generator (B2) is a compound that generates a strong acid when irradiated with light. In the resin film obtained from the composition containing the other acid generator (B2), a cross-linked structure is formed by the acid generated by light irradiation acting on the cross-linking agent (D) described later. Therefore, a negative pattern can be formed by using another acid generator (B2).
《キノンジアジド化合物(B1)》
キノンジアジド化合物(B1)は、例えば、ナフトキノンジアジド化合物が挙げられ、フェノール性水酸基を1つ以上有する化合物と、1,2-ナフトキノンジアジド-4-スルホン酸または1,2-ナフトキノンジアジド-5-スルホン酸とのエステル化合物である。フェノール性水酸基を1つ以上有する化合物の具体例としては、例えば、特開2014-186300号公報の段落[0065]~[0070]に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 << Quinonediazide compound (B1) >>
Examples of the quinone diazide compound (B1) include a naphthoquinone diazide compound, and a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid. And an ester compound. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP 2014-186300 A, which are described in the present specification. It shall be.
キノンジアジド化合物(B1)は、例えば、ナフトキノンジアジド化合物が挙げられ、フェノール性水酸基を1つ以上有する化合物と、1,2-ナフトキノンジアジド-4-スルホン酸または1,2-ナフトキノンジアジド-5-スルホン酸とのエステル化合物である。フェノール性水酸基を1つ以上有する化合物の具体例としては、例えば、特開2014-186300号公報の段落[0065]~[0070]に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 << Quinonediazide compound (B1) >>
Examples of the quinone diazide compound (B1) include a naphthoquinone diazide compound, and a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid. And an ester compound. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP 2014-186300 A, which are described in the present specification. It shall be.
キノンジアジド化合物(B1)の具体例としては、例えば、4,4'-ジヒドロキシジフェニルメタン、4,4'-ジヒドロキシジフェニルエーテル、2,3,4-トリヒドロキシベンゾフェノン、2,3,4,4'-テトラヒドロキシベンゾフェノン、2,3,4,2',4'-ペンタヒドロキシベンゾフェノン、トリス(4-ヒドロキシフェニル)メタン、トリス(4-ヒドロキシフェニル)エタン、1,1-ビス(4-ヒドロキシフェニル)-1-フェニルエタン、1,3-ビス[1-(4-ヒドロキシフェニル)-1-メチルエチル]ベンゼン、1,4-ビス[1-(4-ヒドロキシフェニル)-1-メチルエチル]ベンゼン、4,6-ビス[1-(4-ヒドロキシフェニル)-1-メチルエチル]-1,3-ジヒドロキシベンゼンおよび1,1-ビス(4-ヒドロキシフェニル)-1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エタンから選ばれる化合物と、1,2-ナフトキノンジアジド-4-スルホン酸または1,2-ナフトキノンジアジド-5-スルホン酸とのエステル化合物が挙げられる。
Specific examples of the quinonediazide compound (B1) include, for example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxy. Benzophenone, 2,3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and A compound selected from 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, and 1,2-naphthoquinonediazide-4- And ester compounds with sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid.
キノンジアジド化合物(B1)は1種で用いることができ、または2種以上を併用して用いることができる。
本発明の感光性樹脂組成物において、光酸発生剤(B)としてキノンジアジド化合物(B1)を用いる場合、キノンジアジド化合物(B1)の含有量は、樹脂(A)100質量部に対して、通常は5~50質量部、好ましくは10~40質量部、より好ましくは15~35質量部である。キノンジアジド化合物(B1)の含有量が前記下限値以上であると、未露光部の残膜率が向上し、パターンマスクに忠実な像が得られやすい。キノンジアジド化合物(B1)の含有量が前記上限値以下であると、パターン形状に優れた樹脂膜が得られやすく、製膜時の発泡も防止できる傾向にある。 A quinonediazide compound (B1) can be used by 1 type, or can be used in combination of 2 or more type.
In the photosensitive resin composition of the present invention, when the quinonediazide compound (B1) is used as the photoacid generator (B), the content of the quinonediazide compound (B1) is usually based on 100 parts by mass of the resin (A). The amount is 5 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 15 to 35 parts by mass. When the content of the quinonediazide compound (B1) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved, and an image faithful to the pattern mask is easily obtained. When the content of the quinonediazide compound (B1) is less than or equal to the above upper limit value, a resin film excellent in pattern shape is easily obtained and foaming during film formation tends to be prevented.
本発明の感光性樹脂組成物において、光酸発生剤(B)としてキノンジアジド化合物(B1)を用いる場合、キノンジアジド化合物(B1)の含有量は、樹脂(A)100質量部に対して、通常は5~50質量部、好ましくは10~40質量部、より好ましくは15~35質量部である。キノンジアジド化合物(B1)の含有量が前記下限値以上であると、未露光部の残膜率が向上し、パターンマスクに忠実な像が得られやすい。キノンジアジド化合物(B1)の含有量が前記上限値以下であると、パターン形状に優れた樹脂膜が得られやすく、製膜時の発泡も防止できる傾向にある。 A quinonediazide compound (B1) can be used by 1 type, or can be used in combination of 2 or more type.
In the photosensitive resin composition of the present invention, when the quinonediazide compound (B1) is used as the photoacid generator (B), the content of the quinonediazide compound (B1) is usually based on 100 parts by mass of the resin (A). The amount is 5 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 15 to 35 parts by mass. When the content of the quinonediazide compound (B1) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved, and an image faithful to the pattern mask is easily obtained. When the content of the quinonediazide compound (B1) is less than or equal to the above upper limit value, a resin film excellent in pattern shape is easily obtained and foaming during film formation tends to be prevented.
《他の酸発生剤(B2)》
他の酸発生剤(B2)は、例えば、オニウム塩化合物、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物およびジアゾメタン化合物から選ばれる少なくとも1種である。これらの化合物の具体例としては、例えば、特開2014-186300号公報の段落[0074]~[0079]に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 << Other acid generator (B2) >>
The other acid generator (B2) is, for example, at least one selected from an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
他の酸発生剤(B2)は、例えば、オニウム塩化合物、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物およびジアゾメタン化合物から選ばれる少なくとも1種である。これらの化合物の具体例としては、例えば、特開2014-186300号公報の段落[0074]~[0079]に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 << Other acid generator (B2) >>
The other acid generator (B2) is, for example, at least one selected from an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
本発明の感光性樹脂組成物において、光酸発生剤(B)として他の酸発生剤(B2)を用いる場合、酸発生剤(B2)の含有量は、樹脂(A)100質量部に対して、通常は0.1~10質量部、好ましくは0.3~5質量部、より好ましくは0.5~5質量部である。他の酸発生剤(B2)の含有量が前記下限値以上であると、露光部の硬化が充分となり、耐熱性が向上しやすい。他の酸発生剤(B2)の含有量が前記上限値以下であると、露光光に対する透明性が低下することなく、解像度が高いパターンが得られやすい。
In the photosensitive resin composition of this invention, when using another acid generator (B2) as a photo-acid generator (B), content of an acid generator (B2) is 100 mass parts of resin (A). The amount is usually 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass. When the content of the other acid generator (B2) is equal to or higher than the lower limit, the exposed area is sufficiently cured and the heat resistance is easily improved. When the content of the other acid generator (B2) is not more than the above upper limit value, a pattern with high resolution is easily obtained without lowering the transparency to exposure light.
〈マレイミド基含有化合物(C)〉
本発明の感光性樹脂組成物は、マレイミド基含有化合物(C)を含有する。マレイミド基含有化合物(C)は、マレイミド基を1つ以上、好ましくは2つ以上有する化合物であり、マレイミド基数の上限は好ましくは10、より好ましくは5である。 <Maleimide group-containing compound (C)>
The photosensitive resin composition of the present invention contains a maleimide group-containing compound (C). The maleimide group-containing compound (C) is a compound having one or more maleimide groups, preferably two or more, and the upper limit of the number of maleimide groups is preferably 10, more preferably 5.
本発明の感光性樹脂組成物は、マレイミド基含有化合物(C)を含有する。マレイミド基含有化合物(C)は、マレイミド基を1つ以上、好ましくは2つ以上有する化合物であり、マレイミド基数の上限は好ましくは10、より好ましくは5である。 <Maleimide group-containing compound (C)>
The photosensitive resin composition of the present invention contains a maleimide group-containing compound (C). The maleimide group-containing compound (C) is a compound having one or more maleimide groups, preferably two or more, and the upper limit of the number of maleimide groups is preferably 10, more preferably 5.
マレイミド基は、熱架橋時等においてフェノール性水酸基に直接作用する基であり、例えば以下の反応が進行すると考えられる。この反応では、水酸基が新たに生成するものではなく、またフェノール性水酸基が消費される。
The maleimide group is a group that directly acts on the phenolic hydroxyl group at the time of thermal crosslinking or the like. For example, the following reaction is considered to proceed. In this reaction, hydroxyl groups are not newly generated, and phenolic hydroxyl groups are consumed.
マレイミド基含有化合物(C)としては、マレイミド基を2つ以上有する化合物(C1)(以下、「架橋性マレイミド化合物(C1)」ともいう)が好ましく、前記架橋性マレイミド化合物(C1)としては、例えば、式(C1)で表される化合物が挙げられる。架橋性マレイミド化合物(C1)を用いることで、感光性樹脂組成物から形成される硬化膜は上記薬品耐性の向上効果をより発揮することができる。
As the maleimide group-containing compound (C), a compound (C1) having two or more maleimide groups (hereinafter also referred to as “crosslinkable maleimide compound (C1)”) is preferable. As the crosslinkable maleimide compound (C1), For example, a compound represented by the formula (C1) can be given. By using the crosslinkable maleimide compound (C1), the cured film formed from the photosensitive resin composition can exhibit the effect of improving the chemical resistance.
アルカンジイル基の炭素数は、通常は1~20、好ましくは2~10である。
芳香環含有基および脂環含有基としては、例えば、炭素数6~20のアリーレン基および炭素数3~20のシクロアルキレン基の他、-A-X-A-で表される基、-A-O-A-X-A-O-A-で表される基、-RC2-A-RC2-で表される基が挙げられる。Aはベンゼン環またはシクロヘキサン環であり、それぞれ独立に炭素数1~10のアルキル基および炭素数1~6のアルコキシ基等の置換基を1または2以上有してもよい。Xは、直接結合、-O-、-SO2-、炭素数1~10のアルカンジイル基、または炭素数3~20の脂環含有基である。RC2は炭素数1~10のアルカンジイル基である。 The carbon number of the alkanediyl group is usually 1-20, preferably 2-10.
Examples of the aromatic ring-containing group and alicyclic ring-containing group include a group represented by —A—X—A— in addition to an arylene group having 6 to 20 carbon atoms and a cycloalkylene group having 3 to 20 carbon atoms, —A And a group represented by —O—A—X—A—O—A— and a group represented by —R C2 —A—R C2 —. A is a benzene ring or a cyclohexane ring, and may each independently have one or more substituents such as an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. X is a direct bond, —O—, —SO 2 —, an alkanediyl group having 1 to 10 carbon atoms, or an alicyclic group having 3 to 20 carbon atoms. R C2 is an alkanediyl group having 1 to 10 carbon atoms.
芳香環含有基および脂環含有基としては、例えば、炭素数6~20のアリーレン基および炭素数3~20のシクロアルキレン基の他、-A-X-A-で表される基、-A-O-A-X-A-O-A-で表される基、-RC2-A-RC2-で表される基が挙げられる。Aはベンゼン環またはシクロヘキサン環であり、それぞれ独立に炭素数1~10のアルキル基および炭素数1~6のアルコキシ基等の置換基を1または2以上有してもよい。Xは、直接結合、-O-、-SO2-、炭素数1~10のアルカンジイル基、または炭素数3~20の脂環含有基である。RC2は炭素数1~10のアルカンジイル基である。 The carbon number of the alkanediyl group is usually 1-20, preferably 2-10.
Examples of the aromatic ring-containing group and alicyclic ring-containing group include a group represented by —A—X—A— in addition to an arylene group having 6 to 20 carbon atoms and a cycloalkylene group having 3 to 20 carbon atoms, —A And a group represented by —O—A—X—A—O—A— and a group represented by —R C2 —A—R C2 —. A is a benzene ring or a cyclohexane ring, and may each independently have one or more substituents such as an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. X is a direct bond, —O—, —SO 2 —, an alkanediyl group having 1 to 10 carbon atoms, or an alicyclic group having 3 to 20 carbon atoms. R C2 is an alkanediyl group having 1 to 10 carbon atoms.
アルカンジイル基としては、メチレン基、エタンジイル基、プロパンジイル基、ヘキサンジイル基、オクタンジイル基、ノナンジイル基、デカンジイル基等が挙げられる。アリーレン基としては、フェニレン基、メチルフェニレン基、t-ブチルフェニレン基、ナフチレン基等が挙げられる。シクロアルキレン基としては、シクロブタンジイル基、シクロペンタンジイル基、シクロヘキサンジイル基等が挙げられる。アルキル基としては、メチル基、エチル基、プロピル基等が挙げられる。アルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。脂環としては、シクロヘキサン環、トリシクロデカン環等が挙げられる。
Examples of the alkanediyl group include a methylene group, an ethanediyl group, a propanediyl group, a hexanediyl group, an octanediyl group, a nonanediyl group, and a decanediyl group. Examples of the arylene group include a phenylene group, a methylphenylene group, a t-butylphenylene group, and a naphthylene group. Examples of the cycloalkylene group include a cyclobutanediyl group, a cyclopentanediyl group, and a cyclohexanediyl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alicyclic ring include a cyclohexane ring and a tricyclodecane ring.
架橋性マレイミド化合物(C1)の具体例としては、例えば、
N,N'-エチレンビスマレイミド、
N,N'-ヘキサメチレンビスマレイミド、
N,N'-(2,2,4-トリメチルヘキサン)ビスマレイミド、
N,N'-p-フェニレンビスマレイミド、
N,N'-m-フェニレンビスマレイミド、
N,N'-2,4-トリレンビスマレイミド、
N,N'-2,6-トリレンビスマレイミド、
N,N'-p-キシリレンビスマレイミド、
N,N'-m-キシリレンビスマレイミド、
N,N'-(1,3-ジメチレンシクロヘキサン)ビスマレイミド、
N,N'-(1,4-ジメチレンシクロヘキサン)ビスマレイミド、
N,N'-(4,4'-ビフェニレン)ビスマレイミド、
N,N'-(4,4'-ジフェニルメタン)ビスマレイミド、
N,N'-(4,4'-ジシクロヘキシルメタン)ビスマレイミド、
N,N'-(4,4'-ジフェニルオキシ)ビスマレイミド、
N,N'-(4,4'-ジフェニルスルホン)ビスマレイミド
が挙げられる。 Specific examples of the crosslinkable maleimide compound (C1) include, for example,
N, N′-ethylene bismaleimide,
N, N′-hexamethylene bismaleimide,
N, N ′-(2,2,4-trimethylhexane) bismaleimide,
N, N′-p-phenylenebismaleimide,
N, N′-m-phenylene bismaleimide,
N, N′-2,4-tolylene bismaleimide,
N, N′-2,6-tolylene bismaleimide,
N, N′-p-xylylene bismaleimide,
N, N′-m-xylylene bismaleimide,
N, N ′-(1,3-dimethylenecyclohexane) bismaleimide,
N, N ′-(1,4-dimethylenecyclohexane) bismaleimide,
N, N ′-(4,4′-biphenylene) bismaleimide,
N, N ′-(4,4′-diphenylmethane) bismaleimide,
N, N ′-(4,4′-dicyclohexylmethane) bismaleimide,
N, N ′-(4,4′-diphenyloxy) bismaleimide,
N, N ′-(4,4′-diphenylsulfone) bismaleimide may be mentioned.
N,N'-エチレンビスマレイミド、
N,N'-ヘキサメチレンビスマレイミド、
N,N'-(2,2,4-トリメチルヘキサン)ビスマレイミド、
N,N'-p-フェニレンビスマレイミド、
N,N'-m-フェニレンビスマレイミド、
N,N'-2,4-トリレンビスマレイミド、
N,N'-2,6-トリレンビスマレイミド、
N,N'-p-キシリレンビスマレイミド、
N,N'-m-キシリレンビスマレイミド、
N,N'-(1,3-ジメチレンシクロヘキサン)ビスマレイミド、
N,N'-(1,4-ジメチレンシクロヘキサン)ビスマレイミド、
N,N'-(4,4'-ビフェニレン)ビスマレイミド、
N,N'-(4,4'-ジフェニルメタン)ビスマレイミド、
N,N'-(4,4'-ジシクロヘキシルメタン)ビスマレイミド、
N,N'-(4,4'-ジフェニルオキシ)ビスマレイミド、
N,N'-(4,4'-ジフェニルスルホン)ビスマレイミド
が挙げられる。 Specific examples of the crosslinkable maleimide compound (C1) include, for example,
N, N′-ethylene bismaleimide,
N, N′-hexamethylene bismaleimide,
N, N ′-(2,2,4-trimethylhexane) bismaleimide,
N, N′-p-phenylenebismaleimide,
N, N′-m-phenylene bismaleimide,
N, N′-2,4-tolylene bismaleimide,
N, N′-2,6-tolylene bismaleimide,
N, N′-p-xylylene bismaleimide,
N, N′-m-xylylene bismaleimide,
N, N ′-(1,3-dimethylenecyclohexane) bismaleimide,
N, N ′-(1,4-dimethylenecyclohexane) bismaleimide,
N, N ′-(4,4′-biphenylene) bismaleimide,
N, N ′-(4,4′-diphenylmethane) bismaleimide,
N, N ′-(4,4′-dicyclohexylmethane) bismaleimide,
N, N ′-(4,4′-diphenyloxy) bismaleimide,
N, N ′-(4,4′-diphenylsulfone) bismaleimide may be mentioned.
架橋性マレイミド化合物(C1)のその他の具体例としては、例えば、ビス[4-(4-マレイミドフェノキシ)フェニル]メタン、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパン、ビス[4-(4-マレイミドフェノキシ)フェニル]オクタン、ビス[4-(4-マレイミドフェノキシ)フェニル]デカン、ビス[4-(4-マレイミドフェノキシ)フェニル]シクロヘキサン、ビス[4-(4-マレイミドフェノキシ)フェニル]-トリシクロ-[5.2.1.O2.6]デカンが挙げられる。
Other specific examples of the crosslinkable maleimide compound (C1) include, for example, bis [4- (4-maleimidophenoxy) phenyl] methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] octane, bis [4- (4-maleimidophenoxy) phenyl] decane, bis [4- (4-maleimidophenoxy) phenyl] cyclohexane, bis [4- (4-maleimidophenoxy) ) Phenyl] -tricyclo- [5.2.1. O 2.6 ] decane.
前記例示化合物中のベンゼン環およびシクロヘキサン環における少なくとも1つの水素原子は、それぞれ独立にC1-10アルキル基で置換されていてもよい。アルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。
At least one hydrogen atom in the benzene ring and the cyclohexane ring in the exemplary compound may be independently substituted with a C 1-10 alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
その他、ポリオキシアルキレンジアミンの両末端が無水マレイン酸で封止されたビスマレイミド化合物を用いることもできる。例えば、ポリオキシエチレンジアミンの両末端が無水マレイン酸で封止されたビスマレイミド化合物、ポリオキシプロピレンジアミンの両末端が無水マレイン酸で封止されたビスマレイミド化合物、ポリオキシブチレンジアミンの両末端が無水マレイン酸で封止されたビスマレイミド化合物が挙げられる。
In addition, a bismaleimide compound in which both ends of polyoxyalkylene diamine are sealed with maleic anhydride can also be used. For example, a bismaleimide compound in which both ends of polyoxyethylenediamine are sealed with maleic anhydride, a bismaleimide compound in which both ends of polyoxypropylenediamine are sealed with maleic anhydride, and both ends of polyoxybutylenediamine are anhydrous Examples thereof include bismaleimide compounds sealed with maleic acid.
また、マレイミド基含有化合物(C)としては、マレイミド基を1つ有する化合物(C2)(以下、「非架橋性マレイミド化合物(C2)」ともいう)を用いることもできる。非架橋性マレイミド化合物(C2)を用いる場合も、例えばポストベーク時に樹脂(A)のフェノール性水酸基を消費させることができ、したがって得られる膜の薬品耐性を向上させることができる。また、非架橋性マレイミド化合物(C2)を用いる場合、硬化性の観点から、架橋剤(D)を用いることが好ましい。
Further, as the maleimide group-containing compound (C), a compound (C2) having one maleimide group (hereinafter, also referred to as “non-crosslinkable maleimide compound (C2)”) can be used. Even when the non-crosslinkable maleimide compound (C2) is used, for example, the phenolic hydroxyl group of the resin (A) can be consumed at the time of post-baking, and thus the chemical resistance of the obtained film can be improved. Moreover, when using a non-crosslinkable maleimide compound (C2), it is preferable to use a crosslinking agent (D) from a sclerosing | hardenable viewpoint.
非架橋性マレイミド化合物(C2)としては、例えば、N-フェニルマレイミド、N-o-メチルフェニルマレイミド等のN-C6-20アリールマレイミド;N-メチルマレイミド、N-プロピルマレイミド、N-ブチルマレイミド、N-デシルマレイミド等のN-C1-20アルキルマレイミド;N-シクロヘキシルマレイミド等のN-C3-20シクロアルキルマレイミドが挙げられる。
Non-crosslinkable maleimide compounds (C2) include, for example, N—C 6-20 arylmaleimides such as N-phenylmaleimide and No-methylphenylmaleimide; N-methylmaleimide, N-propylmaleimide, N-butylmaleimide N-C 1-20 alkylmaleimide such as N-decylmaleimide; N-C 3-20 cycloalkylmaleimide such as N-cyclohexylmaleimide.
マレイミド基含有化合物(C)は1種で用いることができ、または2種以上を併用して用いることができる。
本発明の感光性樹脂組成物において、マレイミド基含有化合物(C)の含有量は、樹脂(A)100質量部に対して、通常は0.1~200質量部、好ましくは1~100質量部、より好ましくは5~50質量部である。マレイミド基含有化合物(C)の含有量が前記範囲にあると、感光性樹脂組成物から得られる硬化膜の、薬品耐性とクラック耐性との両立に優れる。 A maleimide group containing compound (C) can be used by 1 type, or can be used in combination of 2 or more type.
In the photosensitive resin composition of the present invention, the content of the maleimide group-containing compound (C) is usually 0.1 to 200 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin (A). More preferably, it is 5 to 50 parts by mass. When the content of the maleimide group-containing compound (C) is in the above range, the cured film obtained from the photosensitive resin composition is excellent in both chemical resistance and crack resistance.
本発明の感光性樹脂組成物において、マレイミド基含有化合物(C)の含有量は、樹脂(A)100質量部に対して、通常は0.1~200質量部、好ましくは1~100質量部、より好ましくは5~50質量部である。マレイミド基含有化合物(C)の含有量が前記範囲にあると、感光性樹脂組成物から得られる硬化膜の、薬品耐性とクラック耐性との両立に優れる。 A maleimide group containing compound (C) can be used by 1 type, or can be used in combination of 2 or more type.
In the photosensitive resin composition of the present invention, the content of the maleimide group-containing compound (C) is usually 0.1 to 200 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin (A). More preferably, it is 5 to 50 parts by mass. When the content of the maleimide group-containing compound (C) is in the above range, the cured film obtained from the photosensitive resin composition is excellent in both chemical resistance and crack resistance.
〈架橋剤(D)〉
本発明の感光性樹脂組成物は、任意成分として、樹脂膜の硬化性を向上させるため、また硬化膜の薬品耐性とクラック耐性との両立のため、架橋剤(D)を含有することができる。ただし、架橋剤(D)からは上述したマレイミド基含有化合物(C)は除く。架橋剤(D)は、樹脂(A)や、架橋剤同士で反応する架橋成分(硬化成分)として作用する。 <Crosslinking agent (D)>
The photosensitive resin composition of the present invention can contain a crosslinking agent (D) as an optional component in order to improve the curability of the resin film and to achieve both chemical resistance and crack resistance of the cured film. . However, the maleimide group-containing compound (C) described above is excluded from the crosslinking agent (D). The crosslinking agent (D) acts as a resin (A) or a crosslinking component (curing component) that reacts with the crosslinking agent.
本発明の感光性樹脂組成物は、任意成分として、樹脂膜の硬化性を向上させるため、また硬化膜の薬品耐性とクラック耐性との両立のため、架橋剤(D)を含有することができる。ただし、架橋剤(D)からは上述したマレイミド基含有化合物(C)は除く。架橋剤(D)は、樹脂(A)や、架橋剤同士で反応する架橋成分(硬化成分)として作用する。 <Crosslinking agent (D)>
The photosensitive resin composition of the present invention can contain a crosslinking agent (D) as an optional component in order to improve the curability of the resin film and to achieve both chemical resistance and crack resistance of the cured film. . However, the maleimide group-containing compound (C) described above is excluded from the crosslinking agent (D). The crosslinking agent (D) acts as a resin (A) or a crosslinking component (curing component) that reacts with the crosslinking agent.
架橋剤(D)は、エポキシ系架橋剤(D1)、および-CH2ORで表される基(前記式中、Rは、水素原子、炭素数1~10のアルキル基または炭素数2~10のアシル基である)を少なくとも2つ有する架橋剤(D2)から選ばれる少なくとも1種の架橋剤を含むことが好ましい。
The crosslinking agent (D) is an epoxy-based crosslinking agent (D1) and a group represented by —CH 2 OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms). It is preferable to include at least one crosslinking agent selected from crosslinking agents (D2) having at least two (which are acyl groups).
エポキシ系架橋剤(D1)としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール-フェノール共縮ノボラック型エポキシ樹脂、ナフトール-クレゾール共縮ノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリスフェノール型エポキシ樹脂、テトラフェノール型エポキシ樹脂、フェノール-キシリレン型エポキシ樹脂、ナフトール-キシリレン型エポキシ樹脂、フェノール-ジシクロペンタジエン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、レゾルシン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族エポキシ樹脂が挙げられる。
Examples of the epoxy-based crosslinking agent (D1) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, Bisphenol type epoxy resin, biphenyl type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin Naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, Call type epoxy resin, dihydroxynaphthalene type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins.
架橋剤(D2)は、-CH2ORで表される基を少なくとも2つ有する。前記式中、Rは、水素原子、炭素数1~10のアルキル基または炭素数2~10のアシル基であり、好ましくは水素原子または炭素数1~6のアルキル基である。前記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。前記アシル基としては、アセチル基等が挙げられる。ここで、-CH2ORで表される基は、熱または酸によりメチレン基が樹脂(A)の芳香環と反応し、架橋反応が進行すると考えられる。
The crosslinking agent (D2) has at least two groups represented by —CH 2 OR. In the above formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acyl group include an acetyl group. Here, in the group represented by —CH 2 OR, it is considered that the methylene group reacts with the aromatic ring of the resin (A) by heat or acid, and the crosslinking reaction proceeds.
架橋剤(D2)としては、例えば、式(d2-1)で表される基を2つ以上有する化合物、式(d2-2)で表される基を2つ以上有する化合物、メチロール基含有フェノール化合物、アルキルメチロール基含有フェノール化合物、アシロキシメチル基含有フェノール化合物が挙げられる。
Examples of the crosslinking agent (D2) include compounds having two or more groups represented by the formula (d2-1), compounds having two or more groups represented by the formula (d2-2), and methylol group-containing phenols. Examples thereof include a compound, an alkylmethylol group-containing phenol compound, and an acyloxymethyl group-containing phenol compound.
架橋剤(D2)としては、例えば、ポリメチロール化メラミン、ポリメチロール化グリコールウリル、ポリメチロール化グアナミン、ポリメチロール化ウレア等の窒素化合物;前記窒素化合物中の活性メチロール基(N原子に結合したCH2OH基)の全部または一部がアルキルエーテル化またはアシロキシ化された化合物が挙げられる。ここで、アルキルエーテルを構成するアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基が挙げられ、これらは互いに同一であってもよいし、異なっていてもよい。また、アルキルエーテル化またはアシロキシ化されていない活性メチロール基は、一分子内で自己縮合することができ、または、二分子間で縮合して、その結果、オリゴマー成分を形成することができる。
Examples of the crosslinking agent (D2) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) 2 OH groups) are all alkyl etherified or acyloxylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other. Also, active methylol groups that are not alkyl etherified or acyloxylated can self-condense within one molecule or condense between two molecules, resulting in the formation of an oligomer component.
架橋剤(D2)としては、例えば、特開平6-180501号公報、特開2006-178059号公報、および特開2012-226297号公報に記載の架橋剤が挙げられる。具体的には、ポリメチロール化メラミン、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシメチルメラミン等のメラミン系架橋剤;ポリメチロール化グリコールウリル、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等のグリコールウリル系架橋剤;3,9-ビス[2-(3,5-ジアミノ-2,4,6-トリアザフェニル)エチル]2,4,8,10-テトラオキソスピロ[5.5]ウンデカン、3,9-ビス[2-(3,5-ジアミノ-2,4,6-トリアザフェニル)プロピル]2,4,8,10-テトラオキソスピロ[5.5]ウンデカン等のグアナミンをメチロール化した化合物、および当該化合物中の活性メチロール基の全部または一部をアルキルエーテル化またはアシロキシ化した化合物等のグアナミン系架橋剤が挙げられる。これらの中でも、メラミン系架橋剤およびグアナミン系架橋剤が好ましい。
Examples of the crosslinking agent (D2) include the crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297. Specifically, melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5.5] undecane A compound obtained by methylolating guanamine, etc., and all of the active methylol groups in the compound Or guanamine-based crosslinking agent such as an alkyl etherified or acyloxy of the compounds of the part. Among these, a melamine type crosslinking agent and a guanamine type crosslinking agent are preferable.
メチロール基含有フェノール化合物、アルキルメチロール基含有フェノール化合物およびアシロキシメチル基含有フェノール化合物としては、例えば、下記式で表される化合物、2,6-ジメトキシメチル-4-t-ブチルフェノール、2,6-ジメトキシメチル-p-クレゾール、2,6-ジアセトキシメチル-p-クレゾールが挙げられる。
Examples of the methylol group-containing phenol compound, the alkylmethylol group-containing phenol compound, and the acyloxymethyl group-containing phenol compound include compounds represented by the following formulas, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6- Examples include dimethoxymethyl-p-cresol and 2,6-diacetoxymethyl-p-cresol.
架橋剤(D)として、エポキシ系架橋剤(D1)および前記架橋剤(D2)以外の他の架橋剤(D3)を用いてもよい。他の架橋剤(D3)としては、例えば、オキセタン環含有化合物、オキサゾリン環含有化合物、イソシアネート基含有化合物(ブロック化されたものを含む。)、アルデヒド基含有フェノール化合物が挙げられる。
As the crosslinking agent (D), a crosslinking agent (D3) other than the epoxy crosslinking agent (D1) and the crosslinking agent (D2) may be used. Examples of the other crosslinking agent (D3) include an oxetane ring-containing compound, an oxazoline ring-containing compound, an isocyanate group-containing compound (including a blocked one), and an aldehyde group-containing phenol compound.
本発明の感光性樹脂組成物において、架橋剤(D)の含有量は、樹脂(A)100質量部に対して、通常は1~60質量部、好ましくは3~50質量部、より好ましくは5~40質量部である。架橋剤(D)の含有量が前記範囲にあると、薬品耐性とクラック耐性との両立に優れた硬化膜が形成される。また、組成物の硬化性に優れる。
In the photosensitive resin composition of the present invention, the content of the crosslinking agent (D) is usually 1 to 60 parts by weight, preferably 3 to 50 parts by weight, more preferably 100 parts by weight of the resin (A). 5 to 40 parts by mass. When the content of the crosslinking agent (D) is in the above range, a cured film excellent in both chemical resistance and crack resistance is formed. Further, the curability of the composition is excellent.
〈溶剤〉
本発明の感光性樹脂組成物は、溶剤を含有することができる。溶剤を用いることで、本発明の感光性樹脂組成物の取扱い性を向上させたり、粘度や保存安定性を調節したりすることができる。 <solvent>
The photosensitive resin composition of the present invention can contain a solvent. By using a solvent, the handleability of the photosensitive resin composition of the present invention can be improved, and the viscosity and storage stability can be adjusted.
本発明の感光性樹脂組成物は、溶剤を含有することができる。溶剤を用いることで、本発明の感光性樹脂組成物の取扱い性を向上させたり、粘度や保存安定性を調節したりすることができる。 <solvent>
The photosensitive resin composition of the present invention can contain a solvent. By using a solvent, the handleability of the photosensitive resin composition of the present invention can be improved, and the viscosity and storage stability can be adjusted.
溶剤としては、例えば、
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類;プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類;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エチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;
エチルセロソルブ、ブチルセロソルブ等のセロソルブ類;ブチルカルビトール等のカルビトール類;乳酸メチル、乳酸エチル、乳酸n-プロピル、乳酸イソプロピル等の乳酸エステル類;酢酸エチル、酢酸n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸イソブチル、酢酸n-アミル、酢酸イソアミル、プロピオン酸イソプロピル、プロピオン酸n-ブチル、プロピオン酸イソブチル等の脂肪族カルボン酸エステル類;3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類;
2-ヘプタノン、3-ヘプタノン、4-ヘプタノン、シクロヘキサノン等のケトン類;N-ジメチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類;
γ-ブチロラクトン等のラクトン類;
トルエン、キシレン等の芳香族炭化水素類;
が挙げられる。 As a solvent, for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Recall monopropyl ether acetates, propylene glycol monoalkyl ether acetate such as propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; Ethyl acetate, n-propyl acetate, isopropyl acetate, n acetate -Aliphatic carboxylic acid esters such as butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Other esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;
Lactones such as γ-butyrolactone;
Aromatic hydrocarbons such as toluene and xylene;
Is mentioned.
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類;プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類;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エチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;
エチルセロソルブ、ブチルセロソルブ等のセロソルブ類;ブチルカルビトール等のカルビトール類;乳酸メチル、乳酸エチル、乳酸n-プロピル、乳酸イソプロピル等の乳酸エステル類;酢酸エチル、酢酸n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸イソブチル、酢酸n-アミル、酢酸イソアミル、プロピオン酸イソプロピル、プロピオン酸n-ブチル、プロピオン酸イソブチル等の脂肪族カルボン酸エステル類;3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類;
2-ヘプタノン、3-ヘプタノン、4-ヘプタノン、シクロヘキサノン等のケトン類;N-ジメチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類;
γ-ブチロラクトン等のラクトン類;
トルエン、キシレン等の芳香族炭化水素類;
が挙げられる。 As a solvent, for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Recall monopropyl ether acetates, propylene glycol monoalkyl ether acetate such as propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; Ethyl acetate, n-propyl acetate, isopropyl acetate, n acetate -Aliphatic carboxylic acid esters such as butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Other esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;
Lactones such as γ-butyrolactone;
Aromatic hydrocarbons such as toluene and xylene;
Is mentioned.
これらの中でも、ラクトン類、乳酸エステル類、プロピレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類が好ましく;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、プロピレングリコールモノメチルエーテルがより好ましい。
Among these, lactones, lactic acid esters, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers are preferable; γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether are more preferable.
溶剤は1種で用いることができ、または2種以上を併用して用いることができる。
溶剤を用いる場合、本発明の感光性樹脂組成物における溶剤の含有割合は、通常は10~95質量%、好ましくは30~90質量%である。 A solvent can be used by 1 type, or can be used in combination of 2 or more types.
When a solvent is used, the content of the solvent in the photosensitive resin composition of the present invention is usually 10 to 95% by mass, preferably 30 to 90% by mass.
溶剤を用いる場合、本発明の感光性樹脂組成物における溶剤の含有割合は、通常は10~95質量%、好ましくは30~90質量%である。 A solvent can be used by 1 type, or can be used in combination of 2 or more types.
When a solvent is used, the content of the solvent in the photosensitive resin composition of the present invention is usually 10 to 95% by mass, preferably 30 to 90% by mass.
〈その他添加剤〉
本発明の感光性樹脂組成物は、その他、密着助剤、架橋微粒子、レベリング剤、界面活性剤、増感剤、無機フィラー、クエンチャー、およびアルカリ溶解性促進剤等の各種添加剤を、本発明の目的および特性を損なわない範囲で含有することができる。 <Other additives>
The photosensitive resin composition of the present invention contains various additives such as adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, and alkali solubility promoters. It can contain in the range which does not impair the objective and characteristic of invention.
本発明の感光性樹脂組成物は、その他、密着助剤、架橋微粒子、レベリング剤、界面活性剤、増感剤、無機フィラー、クエンチャー、およびアルカリ溶解性促進剤等の各種添加剤を、本発明の目的および特性を損なわない範囲で含有することができる。 <Other additives>
The photosensitive resin composition of the present invention contains various additives such as adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, and alkali solubility promoters. It can contain in the range which does not impair the objective and characteristic of invention.
〈感光性樹脂組成物の調製方法〉
本発明の感光性樹脂組成物は、各成分を均一に混合することにより調製できる。また、異物を取り除くために、各成分を均一に混合した後、得られた混合物をフィルター等で濾過してもよい。 <Method for preparing photosensitive resin composition>
The photosensitive resin composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove a foreign material, after mixing each component uniformly, you may filter the obtained mixture with a filter.
本発明の感光性樹脂組成物は、各成分を均一に混合することにより調製できる。また、異物を取り除くために、各成分を均一に混合した後、得られた混合物をフィルター等で濾過してもよい。 <Method for preparing photosensitive resin composition>
The photosensitive resin composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove a foreign material, after mixing each component uniformly, you may filter the obtained mixture with a filter.
〔硬化膜およびその製造方法〕
本発明の硬化膜は、上述の感光性樹脂組成物から形成される。前記感光性樹脂組成物を用いることにより、薬品耐性およびクラック耐性が高く、解像度の高いパターン化硬化膜を製造することができる。 [Curing film and method for producing the same]
The cured film of the present invention is formed from the above-described photosensitive resin composition. By using the photosensitive resin composition, a patterned cured film having high chemical resistance and crack resistance and high resolution can be produced.
本発明の硬化膜は、上述の感光性樹脂組成物から形成される。前記感光性樹脂組成物を用いることにより、薬品耐性およびクラック耐性が高く、解像度の高いパターン化硬化膜を製造することができる。 [Curing film and method for producing the same]
The cured film of the present invention is formed from the above-described photosensitive resin composition. By using the photosensitive resin composition, a patterned cured film having high chemical resistance and crack resistance and high resolution can be produced.
したがって、本発明の感光性樹脂組成物は、硬化膜および絶縁膜の形成に好適に用いることができ、例えば、回路基板(半導体素子)、半導体パッケージまたは表示素子等の電子部品が有する、表面保護膜、層間絶縁膜および平坦化膜等の形成材料や、高密度実装基板用絶縁膜材料として好適に用いることができる。
Therefore, the photosensitive resin composition of the present invention can be suitably used for the formation of a cured film and an insulating film. For example, surface protection possessed by electronic components such as circuit boards (semiconductor elements), semiconductor packages, and display elements. It can be suitably used as a material for forming a film, an interlayer insulating film, a planarizing film, etc., or an insulating film material for a high-density mounting substrate.
本発明の硬化膜の製造例を以下に示す。この製造例は、本発明の感光性樹脂組成物の樹脂膜を支持体上に形成する工程(膜形成工程)、所望のパターンマスクを介して前記樹脂膜を露光する工程(露光工程)、アルカリ性現像液により前記樹脂膜を現像して、ポジ型の場合は露光部を、ネガ型の場合は非露光部を溶解・除去することにより、支持体上に所望のパターン化樹脂膜を形成する工程(現像工程)、および前記パターン化樹脂膜を加熱する工程(加熱工程)を有する。
Examples of production of the cured film of the present invention are shown below. This production example includes a step of forming a resin film of the photosensitive resin composition of the present invention on a support (film formation step), a step of exposing the resin film through a desired pattern mask (exposure step), an alkaline property The step of forming the desired patterned resin film on the support by developing the resin film with a developer and dissolving and removing the exposed portion in the case of the positive type and the non-exposed portion in the case of the negative type. (Developing step) and a step of heating the patterned resin film (heating step).
[1]膜形成工程
膜形成工程では、前記感光性樹脂組成物を、最終的に得られる硬化膜の膜厚が例えば0.1~100μmとなるように、支持体上に塗布する。これをオーブンやホットプレートを用いて、例えば、50~140℃で10~360秒間加熱する(プレベーク)。このようにして支持体上に樹脂膜を形成する。 [1] Film Forming Step In the film forming step, the photosensitive resin composition is coated on a support so that the finally obtained cured film has a thickness of, for example, 0.1 to 100 μm. This is heated using an oven or a hot plate, for example, at 50 to 140 ° C. for 10 to 360 seconds (pre-baking). In this way, a resin film is formed on the support.
膜形成工程では、前記感光性樹脂組成物を、最終的に得られる硬化膜の膜厚が例えば0.1~100μmとなるように、支持体上に塗布する。これをオーブンやホットプレートを用いて、例えば、50~140℃で10~360秒間加熱する(プレベーク)。このようにして支持体上に樹脂膜を形成する。 [1] Film Forming Step In the film forming step, the photosensitive resin composition is coated on a support so that the finally obtained cured film has a thickness of, for example, 0.1 to 100 μm. This is heated using an oven or a hot plate, for example, at 50 to 140 ° C. for 10 to 360 seconds (pre-baking). In this way, a resin film is formed on the support.
支持体としては、例えば、シリコンウエハ、化合物半導体ウエハ、金属薄膜付きウエハ、ガラス基板、石英基板、セラミックス基板、アルミ基板、およびこれらの支持体の表面に半導体チップを有する基板が挙げられる。塗布方法としては、例えば、ディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法、カーテンコート法、グラビア印刷法、シルクスクリーン法、インクジェット法が挙げられる。
Examples of the support include a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor chip on the surface of these supports. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
[2]露光工程
露光工程では、所望のパターンマスクを介して、例えばコンタクトアライナー、ステッパーまたはスキャナーを用いて、前記樹脂膜に対して露光を行う。露光光としては、紫外線、可視光線などが挙げられ、例えば、波長200~500nmの光(例:i線(365nm))を用いる。活性光線の照射量は、前記感光性樹脂組成物中の各成分の種類、配合割合、前記樹脂膜の厚さなどによって異なるが、露光量は通常は100~5,000mJ/cm2である。 [2] Exposure process In the exposure process, the resin film is exposed through a desired pattern mask using, for example, a contact aligner, a stepper, or a scanner. Examples of the exposure light include ultraviolet light and visible light. For example, light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is used. The irradiation amount of actinic rays varies depending on the type of each component in the photosensitive resin composition, the blending ratio, the thickness of the resin film, etc., but the exposure amount is usually 100 to 5,000 mJ / cm 2 .
露光工程では、所望のパターンマスクを介して、例えばコンタクトアライナー、ステッパーまたはスキャナーを用いて、前記樹脂膜に対して露光を行う。露光光としては、紫外線、可視光線などが挙げられ、例えば、波長200~500nmの光(例:i線(365nm))を用いる。活性光線の照射量は、前記感光性樹脂組成物中の各成分の種類、配合割合、前記樹脂膜の厚さなどによって異なるが、露光量は通常は100~5,000mJ/cm2である。 [2] Exposure process In the exposure process, the resin film is exposed through a desired pattern mask using, for example, a contact aligner, a stepper, or a scanner. Examples of the exposure light include ultraviolet light and visible light. For example, light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is used. The irradiation amount of actinic rays varies depending on the type of each component in the photosensitive resin composition, the blending ratio, the thickness of the resin film, etc., but the exposure amount is usually 100 to 5,000 mJ / cm 2 .
また、ネガ型の場合は、露光後に樹脂膜の加熱処理を行うこともできる。加熱処理の条件は、前記感光性樹脂組成物の各成分の含有量および膜厚等によって異なるが、通常は70~150℃、好ましくは80~120℃で、1~60分間程度である。
In the case of a negative type, the resin film can be heat-treated after exposure. The heat treatment conditions vary depending on the content and film thickness of each component of the photosensitive resin composition, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes.
[3]現像工程
現像工程では、アルカリ性現像液により前記樹脂膜を現像して、ポジ型の場合は露光部を、ネガ型の場合は非露光部を溶解・除去することにより、支持体上に所望のパターンを形成する。現像方法としては、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法等が挙げられる。現像条件は、例えば、5~40℃で1~10分間程度である。 [3] Development process In the development process, the resin film is developed with an alkaline developer, and the exposed part is dissolved and removed in the case of the positive type and the non-exposed part in the case of the negative type. A desired pattern is formed. Examples of the development method include shower development, spray development, immersion development, and paddle development. The development conditions are, for example, about 5 to 40 ° C. and about 1 to 10 minutes.
現像工程では、アルカリ性現像液により前記樹脂膜を現像して、ポジ型の場合は露光部を、ネガ型の場合は非露光部を溶解・除去することにより、支持体上に所望のパターンを形成する。現像方法としては、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法等が挙げられる。現像条件は、例えば、5~40℃で1~10分間程度である。 [3] Development process In the development process, the resin film is developed with an alkaline developer, and the exposed part is dissolved and removed in the case of the positive type and the non-exposed part in the case of the negative type. A desired pattern is formed. Examples of the development method include shower development, spray development, immersion development, and paddle development. The development conditions are, for example, about 5 to 40 ° C. and about 1 to 10 minutes.
アルカリ性現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア水、テトラメチルアンモニウムハイドロキサイド、コリン等のアルカリ性化合物を、1~10質量%濃度となるように水に溶解させたアルカリ性水溶液が挙げられる。前記アルカリ性水溶液には、例えば、メタノール、エタノール等の水溶性の有機溶剤および界面活性剤などを適量添加することができる。なお、アルカリ性現像液で樹脂膜を現像した後は、水で洗浄し、乾燥することができる。
Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. is dissolved in water so as to have a concentration of 1 to 10% by mass. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added to the alkaline aqueous solution, for example. In addition, after developing the resin film with an alkaline developer, it can be washed with water and dried.
[4]加熱工程
加熱工程は、例えば絶縁膜としての特性を充分に発現させるために行う工程であり、加熱によりパターンを硬化させる(ポストベーク)。硬化条件は特に限定されないが、硬化膜の用途に応じて、例えば100~350℃の温度で30分~10時間程度加熱する。硬化を充分に進行させたり、パターン形状の変形を防止したりするため、多段階で加熱することができる。
以上のようにして、硬化膜を得ることができる。 [4] Heating step The heating step is a step that is performed, for example, in order to fully develop characteristics as an insulating film, and the pattern is cured by heating (post-baking). The curing conditions are not particularly limited, but for example, heating is performed at a temperature of 100 to 350 ° C. for about 30 minutes to 10 hours depending on the use of the cured film. In order to sufficiently advance the curing or to prevent deformation of the pattern shape, heating can be performed in multiple stages.
As described above, a cured film can be obtained.
加熱工程は、例えば絶縁膜としての特性を充分に発現させるために行う工程であり、加熱によりパターンを硬化させる(ポストベーク)。硬化条件は特に限定されないが、硬化膜の用途に応じて、例えば100~350℃の温度で30分~10時間程度加熱する。硬化を充分に進行させたり、パターン形状の変形を防止したりするため、多段階で加熱することができる。
以上のようにして、硬化膜を得ることができる。 [4] Heating step The heating step is a step that is performed, for example, in order to fully develop characteristics as an insulating film, and the pattern is cured by heating (post-baking). The curing conditions are not particularly limited, but for example, heating is performed at a temperature of 100 to 350 ° C. for about 30 minutes to 10 hours depending on the use of the cured film. In order to sufficiently advance the curing or to prevent deformation of the pattern shape, heating can be performed in multiple stages.
As described above, a cured film can be obtained.
〔電子部品〕
本発明の感光性樹脂組成物を用いれば、上述の硬化膜を有する電子部品、例えば表面保護膜、層間絶縁膜および平坦化膜から選択される1種以上の硬化膜を有する、回路基板(半導体素子)、半導体パッケージまたは表示素子等の電子部品を製造することができる。 [Electronic parts]
When the photosensitive resin composition of the present invention is used, an electronic component having the above-described cured film, for example, a circuit board (semiconductor) having at least one cured film selected from a surface protective film, an interlayer insulating film, and a planarizing film. Element), a semiconductor package, or an electronic component such as a display element.
本発明の感光性樹脂組成物を用いれば、上述の硬化膜を有する電子部品、例えば表面保護膜、層間絶縁膜および平坦化膜から選択される1種以上の硬化膜を有する、回路基板(半導体素子)、半導体パッケージまたは表示素子等の電子部品を製造することができる。 [Electronic parts]
When the photosensitive resin composition of the present invention is used, an electronic component having the above-described cured film, for example, a circuit board (semiconductor) having at least one cured film selected from a surface protective film, an interlayer insulating film, and a planarizing film. Element), a semiconductor package, or an electronic component such as a display element.
以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」の意味で用いる。
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.
1.物性の測定方法
樹脂(A)の重量平均分子量(Mw)の測定方法
下記条件下でゲルパーミエーションクロマトグラフィー法にてMwを測定した。
・カラム:東ソー社製カラムのTSK-M およびTSK2500を直列に接続
・溶媒:テトラヒドロフラン
・温度:40℃
・検出方法:屈折率法
・標準物質:ポリスチレン
・GPC装置:東ソー製、装置名「HLC-8220-GPC」
樹脂(A)の構造単位の含有量の測定方法
構造単位の含有量は、13C-NMRにより測定した。 1. Method for measuring physical properties Method for measuring weight average molecular weight (Mw) of resin (A) Mw was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Solvent: Tetrahydrofuran Temperature: 40 ° C
-Detection method: Refractive index method-Standard material: Polystyrene-GPC device: manufactured by Tosoh, device name "HLC-8220-GPC"
Method for Measuring Content of Structural Unit of Resin (A) The content of the structural unit was measured by 13 C-NMR.
樹脂(A)の重量平均分子量(Mw)の測定方法
下記条件下でゲルパーミエーションクロマトグラフィー法にてMwを測定した。
・カラム:東ソー社製カラムのTSK-M およびTSK2500を直列に接続
・溶媒:テトラヒドロフラン
・温度:40℃
・検出方法:屈折率法
・標準物質:ポリスチレン
・GPC装置:東ソー製、装置名「HLC-8220-GPC」
樹脂(A)の構造単位の含有量の測定方法
構造単位の含有量は、13C-NMRにより測定した。 1. Method for measuring physical properties Method for measuring weight average molecular weight (Mw) of resin (A) Mw was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Solvent: Tetrahydrofuran Temperature: 40 ° C
-Detection method: Refractive index method-Standard material: Polystyrene-GPC device: manufactured by Tosoh, device name "HLC-8220-GPC"
Method for Measuring Content of Structural Unit of Resin (A) The content of the structural unit was measured by 13 C-NMR.
2.樹脂(A)の合成
[合成例1]共重合体(a-1)の合成
p-t-ブトキシスチレン70部と、スチレン10部とを、プロピレングリコールモノメチルエーテル150部に溶解させ、窒素雰囲気下、反応温度を70℃に保持して、アゾビスイソブチロニトリル4部を用いて10時間重合させた。その後、反応溶液に硫酸を加えて反応温度を90℃に保持して10時間反応させ、p-t-ブトキシスチレン単位を脱保護してp-ヒドロキシスチレン単位に変換した。得られた共重合体に酢酸エチルを加え、水洗を5回繰り返し、酢酸エチル層を分取し、溶剤を除去して、p-ヒドロキシスチレン/スチレン共重合体(a-1)を得た。 2. Synthesis of Resin (A) [Synthesis Example 1] Synthesis of Copolymer (a-1) 70 parts of pt-butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and the reaction was performed in a nitrogen atmosphere. While maintaining the reaction temperature at 70 ° C., polymerization was carried out for 10 hours using 4 parts of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-hydroxystyrene unit. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate layer was separated, and the solvent was removed to obtain a p-hydroxystyrene / styrene copolymer (a-1).
[合成例1]共重合体(a-1)の合成
p-t-ブトキシスチレン70部と、スチレン10部とを、プロピレングリコールモノメチルエーテル150部に溶解させ、窒素雰囲気下、反応温度を70℃に保持して、アゾビスイソブチロニトリル4部を用いて10時間重合させた。その後、反応溶液に硫酸を加えて反応温度を90℃に保持して10時間反応させ、p-t-ブトキシスチレン単位を脱保護してp-ヒドロキシスチレン単位に変換した。得られた共重合体に酢酸エチルを加え、水洗を5回繰り返し、酢酸エチル層を分取し、溶剤を除去して、p-ヒドロキシスチレン/スチレン共重合体(a-1)を得た。 2. Synthesis of Resin (A) [Synthesis Example 1] Synthesis of Copolymer (a-1) 70 parts of pt-butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and the reaction was performed in a nitrogen atmosphere. While maintaining the reaction temperature at 70 ° C., polymerization was carried out for 10 hours using 4 parts of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-hydroxystyrene unit. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate layer was separated, and the solvent was removed to obtain a p-hydroxystyrene / styrene copolymer (a-1).
共重合体(a-1)の重量平均分子量(Mw)は10,000であった。また、共重合体(a-1)はp-ヒドロキシスチレン単位を80モル%、スチレン単位を20モル%有する共重合体であった。
The weight average molecular weight (Mw) of the copolymer (a-1) was 10,000. The copolymer (a-1) was a copolymer having 80 mol% of p-hydroxystyrene units and 20 mol% of styrene units.
3.感光性樹脂組成物の製造
[実施例1]
樹脂(A)として合成例1の共重合体(a-1)95部、光酸発生剤(B)として1,1-ビス(4-ヒドロキシフェニル)-1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エタンと1,2-ナフトキノンジアジド-5-スルホン酸との縮合物(モル比=1:2)(b-1)27.5部、マレイミド基含有化合物(C)として4,4'-ビフェニルメタンビスマレイミド(c-1)30部、および架橋剤(D)としてジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル(日本化薬社製、商品名「XD-1000」)(d-1)10部をγ-ブチロラクトン300部に均一に溶解し、次いで、溶液からメンブランフィルターで異物を除去し、実施例1の感光性樹脂組成物を製造した。得られた感光性樹脂組成物を用いて、所定の評価を行った。 3. Production of photosensitive resin composition [Example 1]
95 parts of the copolymer (a-1) of Synthesis Example 1 as the resin (A) and 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4) as the photoacid generator (B) -Hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid condensate (molar ratio = 1: 2) (b-1) 27.5 parts, containing maleimide group 30 parts of 4,4′-biphenylmethane bismaleimide (c-1) as the compound (C) and polyglycidyl ether of dicyclopentadiene / phenol polymer as the cross-linking agent (D) (trade name “Nippon Kayaku Co., Ltd. XD-1000 ”) (d-1) 10 parts was uniformly dissolved in 300 parts of γ-butyrolactone, and then foreign matters were removed from the solution with a membrane filter to produce a photosensitive resin composition of Example 1. Predetermined evaluation was performed using the obtained photosensitive resin composition.
[実施例1]
樹脂(A)として合成例1の共重合体(a-1)95部、光酸発生剤(B)として1,1-ビス(4-ヒドロキシフェニル)-1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エタンと1,2-ナフトキノンジアジド-5-スルホン酸との縮合物(モル比=1:2)(b-1)27.5部、マレイミド基含有化合物(C)として4,4'-ビフェニルメタンビスマレイミド(c-1)30部、および架橋剤(D)としてジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル(日本化薬社製、商品名「XD-1000」)(d-1)10部をγ-ブチロラクトン300部に均一に溶解し、次いで、溶液からメンブランフィルターで異物を除去し、実施例1の感光性樹脂組成物を製造した。得られた感光性樹脂組成物を用いて、所定の評価を行った。 3. Production of photosensitive resin composition [Example 1]
95 parts of the copolymer (a-1) of Synthesis Example 1 as the resin (A) and 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4) as the photoacid generator (B) -Hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid condensate (molar ratio = 1: 2) (b-1) 27.5 parts, containing maleimide group 30 parts of 4,4′-biphenylmethane bismaleimide (c-1) as the compound (C) and polyglycidyl ether of dicyclopentadiene / phenol polymer as the cross-linking agent (D) (trade name “Nippon Kayaku Co., Ltd. XD-1000 ”) (d-1) 10 parts was uniformly dissolved in 300 parts of γ-butyrolactone, and then foreign matters were removed from the solution with a membrane filter to produce a photosensitive resin composition of Example 1. Predetermined evaluation was performed using the obtained photosensitive resin composition.
[実施例2~11、および比較例1~3]
下記表1に示す成分を用いる以外は、実施例1と同様に各成分を溶剤に均一に混合し、実施例2~11、および比較例1~3の感光性樹脂組成物を調製した。得られた感光性樹脂組成物を用いて、所定の評価を行った。 [Examples 2 to 11 and Comparative Examples 1 to 3]
Except for using the components shown in Table 1 below, each component was uniformly mixed with a solvent in the same manner as in Example 1 to prepare photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 3. Predetermined evaluation was performed using the obtained photosensitive resin composition.
下記表1に示す成分を用いる以外は、実施例1と同様に各成分を溶剤に均一に混合し、実施例2~11、および比較例1~3の感光性樹脂組成物を調製した。得られた感光性樹脂組成物を用いて、所定の評価を行った。 [Examples 2 to 11 and Comparative Examples 1 to 3]
Except for using the components shown in Table 1 below, each component was uniformly mixed with a solvent in the same manner as in Example 1 to prepare photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 3. Predetermined evaluation was performed using the obtained photosensitive resin composition.
表1中に記載の成分の詳細を下記に示す。
《樹脂(A)》
a-1:合成例1の共重合体(a-1)
a-2:クレゾールノボラック樹脂(m-クレゾール:p-クレゾール=6:4(モル比)、ポリスチレン換算重量平均分子量=6,000)
《光酸発生剤(B)》
b-1:1,1-ビス(4-ヒドロキシフェニル)-1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エタンと1,2-ナフトキノンジアジド-5-スルホン酸との縮合物(モル比=1:2)
《マレイミド基含有化合物(C)》
c-1:4,4'-ビフェニルメタンビスマレイミド
c-2:N,N’-m-フェニレンビスマレイミド
c-3:1,6-ビスマレイミド-(2,2,4-トリメチル)ヘキサン
《架橋剤(D)》
d-1:ジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル(日本化薬社製、商品名「XD-1000」)
d-2:下記式に示すポリメチロール化メラミン系架橋剤 Details of the components described in Table 1 are shown below.
<< Resin (A) >>
a-1: Copolymer of Synthesis Example 1 (a-1)
a-2: Cresol novolak resin (m-cresol: p-cresol = 6: 4 (molar ratio), weight average molecular weight in terms of polystyrene = 6,000)
<< Photoacid generator (B) >>
b-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid (molar ratio = 1: 2)
<< Maleimide group-containing compound (C) >>
c-1: 4,4′-biphenylmethane bismaleimide c-2: N, N′-m-phenylene bismaleimide c-3: 1,6-bismaleimide- (2,2,4-trimethyl) hexane << crosslinking Agent (D) >>
d-1: Polyglycidyl ether of dicyclopentadiene / phenol polymer (trade name “XD-1000” manufactured by Nippon Kayaku Co., Ltd.)
d-2: a polymethylolated melamine crosslinking agent represented by the following formula
《樹脂(A)》
a-1:合成例1の共重合体(a-1)
a-2:クレゾールノボラック樹脂(m-クレゾール:p-クレゾール=6:4(モル比)、ポリスチレン換算重量平均分子量=6,000)
《光酸発生剤(B)》
b-1:1,1-ビス(4-ヒドロキシフェニル)-1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エタンと1,2-ナフトキノンジアジド-5-スルホン酸との縮合物(モル比=1:2)
《マレイミド基含有化合物(C)》
c-1:4,4'-ビフェニルメタンビスマレイミド
c-2:N,N’-m-フェニレンビスマレイミド
c-3:1,6-ビスマレイミド-(2,2,4-トリメチル)ヘキサン
《架橋剤(D)》
d-1:ジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル(日本化薬社製、商品名「XD-1000」)
d-2:下記式に示すポリメチロール化メラミン系架橋剤 Details of the components described in Table 1 are shown below.
<< Resin (A) >>
a-1: Copolymer of Synthesis Example 1 (a-1)
a-2: Cresol novolak resin (m-cresol: p-cresol = 6: 4 (molar ratio), weight average molecular weight in terms of polystyrene = 6,000)
<< Photoacid generator (B) >>
b-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid (molar ratio = 1: 2)
<< Maleimide group-containing compound (C) >>
c-1: 4,4′-biphenylmethane bismaleimide c-2: N, N′-m-phenylene bismaleimide c-3: 1,6-bismaleimide- (2,2,4-trimethyl) hexane << crosslinking Agent (D) >>
d-1: Polyglycidyl ether of dicyclopentadiene / phenol polymer (trade name “XD-1000” manufactured by Nippon Kayaku Co., Ltd.)
d-2: a polymethylolated melamine crosslinking agent represented by the following formula
e-1(密着助剤):トリス(トリメトキシシリルプロピル)イソシアヌレート
e-2(アルカリ溶解性促進剤):4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エチリデン]ビスフェノール
《溶剤(F)》
f-1:γ-ブチロラクトン
f-2:乳酸エチル
e-1 (adhesion aid): tris (trimethoxysilylpropyl) isocyanurate e-2 (alkali solubility promoter): 4,4 ′-[1- [4- [1- (4-hydroxyphenyl)- 1-methylethyl] phenyl] ethylidene] bisphenol << solvent (F) >>
f-1: γ-butyrolactone f-2: ethyl lactate
4.評価
感光性樹脂組成物の評価方法は以下のとおりである。 4). The evaluation method of the evaluation photosensitive resin composition is as follows.
感光性樹脂組成物の評価方法は以下のとおりである。 4). The evaluation method of the evaluation photosensitive resin composition is as follows.
4-1.解像性
感光性樹脂組成物を6インチのシリコンウエハにスピンコートし、その後、ホットプレートを用いて120℃で3分間加熱し、厚さ7μmの均一な樹脂膜を作製した。次いで、アライナー(SussMicrotec社製、型式「MA-150」)を用い、高圧水銀灯からの紫外線を、パターンマスクを介して、波長350nmにおける露光量が800mJ/cm2で樹脂膜に照射した。次いで、樹脂膜を、2.38質量%濃度のテトラメチルアンモニウムハイドロキサイド水溶液を用いて23℃で240秒間、浸漬現像した。次いで、現像後の樹脂膜を、超純水にて60秒間洗浄し、エアーにて風乾した後、光学顕微鏡にて観察し、解像した最小パターンのパターン寸法を解像度とした。 4-1. The resolution photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and then heated at 120 ° C. for 3 minutes using a hot plate to prepare a uniform resin film having a thickness of 7 μm. Next, using an aligner (manufactured by Suss Microtec, model “MA-150”), ultraviolet rays from a high-pressure mercury lamp were irradiated to the resin film through a pattern mask at an exposure dose of 800 mJ / cm 2 at a wavelength of 350 nm. Next, the resin film was subjected to immersion development for 240 seconds at 23 ° C. using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass. Next, the developed resin film was washed with ultrapure water for 60 seconds, air-dried with air, then observed with an optical microscope, and the resolution of the minimum pattern size resolved was defined as the resolution.
感光性樹脂組成物を6インチのシリコンウエハにスピンコートし、その後、ホットプレートを用いて120℃で3分間加熱し、厚さ7μmの均一な樹脂膜を作製した。次いで、アライナー(SussMicrotec社製、型式「MA-150」)を用い、高圧水銀灯からの紫外線を、パターンマスクを介して、波長350nmにおける露光量が800mJ/cm2で樹脂膜に照射した。次いで、樹脂膜を、2.38質量%濃度のテトラメチルアンモニウムハイドロキサイド水溶液を用いて23℃で240秒間、浸漬現像した。次いで、現像後の樹脂膜を、超純水にて60秒間洗浄し、エアーにて風乾した後、光学顕微鏡にて観察し、解像した最小パターンのパターン寸法を解像度とした。 4-1. The resolution photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and then heated at 120 ° C. for 3 minutes using a hot plate to prepare a uniform resin film having a thickness of 7 μm. Next, using an aligner (manufactured by Suss Microtec, model “MA-150”), ultraviolet rays from a high-pressure mercury lamp were irradiated to the resin film through a pattern mask at an exposure dose of 800 mJ / cm 2 at a wavelength of 350 nm. Next, the resin film was subjected to immersion development for 240 seconds at 23 ° C. using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass. Next, the developed resin film was washed with ultrapure water for 60 seconds, air-dried with air, then observed with an optical microscope, and the resolution of the minimum pattern size resolved was defined as the resolution.
4-2.薬品耐性
感光性樹脂組成物を4インチのシリコンウエハに塗布し、ホットプレートを用いて120℃で3分間加熱し、厚さ10μmの樹脂膜を作製した。その後、対流式オーブンにて、120℃で30分間、150℃で30分間、さらに実施例1、2、および比較例1では250℃で1時間、実施例3~11、ならびに比較例2および3では200℃で1時間加熱して硬化膜を得た。得られた硬化膜に、フラックス(製品名「WF-6317」、千住金属(株)社製)を塗布し、窒素雰囲気下、260℃に加熱したリフロー装置(型式「STR-2010N2M-III」、千住金属(株)社製)で3分間加熱し、硬化膜の膨潤率(%)((浸漬後の膜厚-浸漬前の膜厚)/浸漬前の膜厚×100(%))を測定した。 4-2. The chemical-resistant photosensitive resin composition was applied to a 4-inch silicon wafer and heated at 120 ° C. for 3 minutes using a hot plate to prepare a resin film having a thickness of 10 μm. Thereafter, in a convection oven at 120 ° C. for 30 minutes, at 150 ° C. for 30 minutes, and in Examples 1, 2 and Comparative Example 1 at 250 ° C. for 1 hour, Examples 3 to 11 and Comparative Examples 2 and 3 Then, it heated at 200 degreeC for 1 hour, and obtained the cured film. A flux (product name “WF-6317”, manufactured by Senju Metal Co., Ltd.) was applied to the resulting cured film and heated to 260 ° C. in a nitrogen atmosphere (model “STR-2010N2M-III”), Heated with Senju Metal Co., Ltd. for 3 minutes and measured swelling ratio (%) of cured film ((film thickness after immersion−film thickness before immersion) / film thickness before immersion × 100 (%)) did.
感光性樹脂組成物を4インチのシリコンウエハに塗布し、ホットプレートを用いて120℃で3分間加熱し、厚さ10μmの樹脂膜を作製した。その後、対流式オーブンにて、120℃で30分間、150℃で30分間、さらに実施例1、2、および比較例1では250℃で1時間、実施例3~11、ならびに比較例2および3では200℃で1時間加熱して硬化膜を得た。得られた硬化膜に、フラックス(製品名「WF-6317」、千住金属(株)社製)を塗布し、窒素雰囲気下、260℃に加熱したリフロー装置(型式「STR-2010N2M-III」、千住金属(株)社製)で3分間加熱し、硬化膜の膨潤率(%)((浸漬後の膜厚-浸漬前の膜厚)/浸漬前の膜厚×100(%))を測定した。 4-2. The chemical-resistant photosensitive resin composition was applied to a 4-inch silicon wafer and heated at 120 ° C. for 3 minutes using a hot plate to prepare a resin film having a thickness of 10 μm. Thereafter, in a convection oven at 120 ° C. for 30 minutes, at 150 ° C. for 30 minutes, and in Examples 1, 2 and Comparative Example 1 at 250 ° C. for 1 hour, Examples 3 to 11 and Comparative Examples 2 and 3 Then, it heated at 200 degreeC for 1 hour, and obtained the cured film. A flux (product name “WF-6317”, manufactured by Senju Metal Co., Ltd.) was applied to the resulting cured film and heated to 260 ° C. in a nitrogen atmosphere (model “STR-2010N2M-III”), Heated with Senju Metal Co., Ltd. for 3 minutes and measured swelling ratio (%) of cured film ((film thickness after immersion−film thickness before immersion) / film thickness before immersion × 100 (%)) did.
4-3.クラック耐性
クラック耐性の評価は貯蔵弾性率(E')を測定することで行った。
離型材付き基板上に感光性樹脂組成物を塗布し、ホットプレートを用いて120℃で5分間加熱し、厚さ15μmの均一な樹脂膜を形成した。次いで、窒素雰囲気下、前記樹脂膜を対流式オーブンにて、120℃で30分間、150℃で30分間、さらに実施例1、2、および比較例1では250℃で1時間、実施例3~11、ならびに比較例2および3では200℃で1時間加熱して硬化膜を形成した。 4-3. Crack resistance The crack resistance was evaluated by measuring the storage elastic modulus (E ′).
A photosensitive resin composition was applied onto a substrate with a release material, and heated at 120 ° C. for 5 minutes using a hot plate to form a uniform resin film having a thickness of 15 μm. Next, in a nitrogen atmosphere, the resin film was subjected to convection oven at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and in Examples 1 and 2 and Comparative Example 1, 250 ° C. for 1 hour. 11 and Comparative Examples 2 and 3 were heated at 200 ° C. for 1 hour to form a cured film.
クラック耐性の評価は貯蔵弾性率(E')を測定することで行った。
離型材付き基板上に感光性樹脂組成物を塗布し、ホットプレートを用いて120℃で5分間加熱し、厚さ15μmの均一な樹脂膜を形成した。次いで、窒素雰囲気下、前記樹脂膜を対流式オーブンにて、120℃で30分間、150℃で30分間、さらに実施例1、2、および比較例1では250℃で1時間、実施例3~11、ならびに比較例2および3では200℃で1時間加熱して硬化膜を形成した。 4-3. Crack resistance The crack resistance was evaluated by measuring the storage elastic modulus (E ′).
A photosensitive resin composition was applied onto a substrate with a release material, and heated at 120 ° C. for 5 minutes using a hot plate to form a uniform resin film having a thickness of 15 μm. Next, in a nitrogen atmosphere, the resin film was subjected to convection oven at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and in Examples 1 and 2 and Comparative Example 1, 250 ° C. for 1 hour. 11 and Comparative Examples 2 and 3 were heated at 200 ° C. for 1 hour to form a cured film.
前記離型材付き基板から、前記硬化膜を剥がし、硬化膜を2.5cm×0.3cmの短冊状に切断した。短冊状の硬化膜の貯蔵弾性率(E')をTMA装置(装置名「TMA/SS6100」、エスアイアイ・ナノテクノロジー(株)社製)にて測定した。測定時の条件は以下の通りである。
チャック距離:2cm
測定周波数:0.1Hz
測定温度範囲:23~330℃ 、昇温スピード:5℃/分 The cured film was peeled off from the substrate with the release material, and the cured film was cut into a 2.5 cm × 0.3 cm strip shape. The storage elastic modulus (E ′) of the strip-like cured film was measured with a TMA device (device name “TMA / SS6100”, manufactured by SII Nanotechnology Co., Ltd.). The measurement conditions are as follows.
Chuck distance: 2cm
Measurement frequency: 0.1 Hz
Measurement temperature range: 23-330 ° C, temperature rising speed: 5 ° C / min
チャック距離:2cm
測定周波数:0.1Hz
測定温度範囲:23~330℃ 、昇温スピード:5℃/分 The cured film was peeled off from the substrate with the release material, and the cured film was cut into a 2.5 cm × 0.3 cm strip shape. The storage elastic modulus (E ′) of the strip-like cured film was measured with a TMA device (device name “TMA / SS6100”, manufactured by SII Nanotechnology Co., Ltd.). The measurement conditions are as follows.
Chuck distance: 2cm
Measurement frequency: 0.1 Hz
Measurement temperature range: 23-330 ° C, temperature rising speed: 5 ° C / min
マレイミド基含有化合物(C)を含有する感光性樹脂組成物から得られる硬化膜は、マレイミド基含有化合物(C)を含有しない感光性樹脂組成物から得られる硬化膜に比べ、同等の薬品耐性であっても、硬化温度以上(実施例1~2、および比較例1は250℃以上、実施例3~11、および比較例2~3は200℃以上)の高温領域における貯蔵弾性率(E')が低く、つまり架橋密度が低いため、クラック耐性に優れていると判断される。
The cured film obtained from the photosensitive resin composition containing the maleimide group-containing compound (C) is equivalent in chemical resistance to the cured film obtained from the photosensitive resin composition not containing the maleimide group-containing compound (C). Even in this case, the storage elastic modulus (E ′ in the high temperature region above the curing temperature (Examples 1 and 2 and Comparative Example 1 is 250 ° C. or higher, Examples 3 to 11 and Comparative Examples 2 and 3 are 200 ° C. or higher). ) Is low, that is, since the crosslink density is low, it is judged to be excellent in crack resistance.
Claims (8)
- フェノール性水酸基を有する樹脂(A)と、
光酸発生剤(B)と、
マレイミド基含有化合物(C)と、
を含有する感光性樹脂組成物。 A resin (A) having a phenolic hydroxyl group;
A photoacid generator (B);
A maleimide group-containing compound (C);
Containing a photosensitive resin composition. - 前記マレイミド基含有化合物(C)が、マレイミド基を2つ以上有する化合物(C1)を含む請求項1に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the maleimide group-containing compound (C) includes a compound (C1) having two or more maleimide groups.
- さらに、架橋剤(D)(だだし、マレイミド基含有化合物(C)を除く)を含有する、請求項1または2に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, further comprising a crosslinking agent (D) (but excluding the maleimide group-containing compound (C)).
- 前記架橋剤(D)が、
エポキシ系架橋剤(D1)、および
-CH2ORで表される基(前記式中、Rは、水素原子、炭素数1~10のアルキル基または炭素数2~10のアシル基である)を少なくとも2つ有する架橋剤(D2)から選ばれる少なくとも1種の架橋剤を含む
請求項3に記載の感光性樹脂組成物。 The crosslinking agent (D) is
An epoxy-based crosslinking agent (D1), and a group represented by —CH 2 OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms). The photosensitive resin composition of Claim 3 containing the at least 1 sort (s) of crosslinking agent chosen from the crosslinking agent (D2) which has at least two. - 前記光酸発生剤(B)が、キノンジアジド化合物(B1)を含む、請求項1~4のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the photoacid generator (B) contains a quinonediazide compound (B1).
- 請求項1~5のいずれか1項に記載の感光性樹脂組成物の樹脂膜を支持体上に形成する工程、前記樹脂膜を露光する工程、アルカリ性現像液により前記樹脂膜を現像してパターン化樹脂膜を形成する工程、および前記パターン化樹脂膜を加熱する工程を有する硬化膜の製造方法。 A step of forming a resin film of the photosensitive resin composition according to any one of claims 1 to 5 on a support, a step of exposing the resin film, and developing the resin film with an alkaline developer to form a pattern The manufacturing method of the cured film which has the process of forming a forming resin film, and the process of heating the said patterned resin film.
- 請求項1~5のいずれか1項に記載の感光性樹脂組成物から形成される硬化膜。 A cured film formed from the photosensitive resin composition according to any one of claims 1 to 5.
- 請求項7の硬化膜を有する電子部品。 An electronic component having the cured film according to claim 7.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05257273A (en) * | 1992-03-11 | 1993-10-08 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2009222923A (en) * | 2008-03-14 | 2009-10-01 | Nagase Chemtex Corp | Radiation-sensitive resin composition |
JP2013190689A (en) * | 2012-03-14 | 2013-09-26 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern-manufacturing method, and semiconductor device |
JP2013190698A (en) * | 2012-03-14 | 2013-09-26 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern-manufacturing method, and semiconductor device |
JP2015145912A (en) * | 2014-01-31 | 2015-08-13 | 昭和電工株式会社 | radiation-sensitive composition |
JP2017129768A (en) * | 2016-01-21 | 2017-07-27 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured product, cured film, display device, and touch panel |
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JP2015196764A (en) * | 2014-04-01 | 2015-11-09 | 太陽インキ製造株式会社 | Curable resin composition, composition for forming permanent coating film, dry film, and printed wiring board |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05257273A (en) * | 1992-03-11 | 1993-10-08 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2009222923A (en) * | 2008-03-14 | 2009-10-01 | Nagase Chemtex Corp | Radiation-sensitive resin composition |
JP2013190689A (en) * | 2012-03-14 | 2013-09-26 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern-manufacturing method, and semiconductor device |
JP2013190698A (en) * | 2012-03-14 | 2013-09-26 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern-manufacturing method, and semiconductor device |
JP2015145912A (en) * | 2014-01-31 | 2015-08-13 | 昭和電工株式会社 | radiation-sensitive composition |
JP2017129768A (en) * | 2016-01-21 | 2017-07-27 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured product, cured film, display device, and touch panel |
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