WO2009133843A1 - Radiation-sensitive resin composition, laminate and method for producing the same, and semiconductor device - Google Patents

Radiation-sensitive resin composition, laminate and method for producing the same, and semiconductor device Download PDF

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Publication number
WO2009133843A1
WO2009133843A1 PCT/JP2009/058262 JP2009058262W WO2009133843A1 WO 2009133843 A1 WO2009133843 A1 WO 2009133843A1 JP 2009058262 W JP2009058262 W JP 2009058262W WO 2009133843 A1 WO2009133843 A1 WO 2009133843A1
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Prior art keywords
group
compound
resin composition
acid
resin
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PCT/JP2009/058262
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French (fr)
Japanese (ja)
Inventor
幸枝 磯貝
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日本ゼオン株式会社
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Priority to CN200980124825.1A priority Critical patent/CN102076774B/en
Priority to JP2010510112A priority patent/JP5488460B2/en
Publication of WO2009133843A1 publication Critical patent/WO2009133843A1/en

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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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

Definitions

  • the present invention relates to a resin composition and a laminate having a resin film obtained from the resin composition on a substrate, and more particularly, a resin suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements.
  • the present invention relates to a composition, a laminate having a resin film obtained from the resin composition on a substrate, a method for producing the same, and a semiconductor device.
  • Various resin films are provided as a film and an electric insulating film for maintaining electric insulation.
  • a resin film as an interlayer insulating film is provided in an element such as a thin film transistor type liquid crystal display element or an integrated circuit element in order to insulate a plurality of wirings arranged in layers.
  • thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films.
  • Patent Document 1 includes a cyclic olefin polymer as a binder resin, a radiation-sensitive compound, an organic solvent, trimethoxysilylbenzoic acid as a compound having an acidic group, and a silicon atom.
  • a radiation-sensitive composition comprising ⁇ -glycidoxypropyltrimethoxysilane, which is a compound having a bound hydrocarbyloxy group, is disclosed.
  • Patent Document 2 contains an organic insulating polymer represented by Formula (1) as a binder resin, a photoacid generator as a radiation-sensitive compound, an organic solvent, and phthalic acid as a compound having two acidic groups.
  • a radiation sensitive composition is disclosed. According to Patent Document 2, it is described that the radiation-sensitive composition can improve electrical characteristics while enabling fine pattern formation.
  • JP 2005-292277 A Japanese Patent Laying-Open No. 2005-171259 (US Patent Application Publication No. 2005/127355)
  • the radiation-sensitive composition described in Patent Document 1 contains an adhesion aid in practice, but still has insufficient adhesion to the substrate, and the sensitivity described in Patent Document 2. It has been found that the radiation composition also has insufficient adhesion to the substrate, and further improvement is necessary. Accordingly, an object of the present invention is to provide a resin composition that is excellent in heat resistance, solvent resistance, surface hardness, insulation, flatness, transparency, chemical resistance, low dielectric property, etc., and has improved adhesion. It is to provide. Furthermore, the other object of this invention is to provide the laminated body which formed the resin film which uses this resin composition on a board
  • the binder resin (A) has a compound (B) having an acidic group, an organic solvent (C), a silicon atom, a titanium atom, and aluminum.
  • a compound (D) having a hydrocarbyloxy group or a hydroxy group bonded to the atom, and the compound (C) having an acidic group is an aliphatic compound, an aromatic compound, and a heterocyclic compound.
  • the resin composition of the present invention preferably further comprises a radiation sensitive compound (E).
  • the acidic group of the compound (B) having an acidic group is preferably a carboxy group, a thiol group, or a carboxymethylenethio group.
  • the acid group acid dissociation constant pKa (the first acid dissociation constant pKa1 when there are two or more acidic groups) of the compound (B) having an acidic group is 3.5 or more and 5. It is preferably in the range of 0 or less.
  • the compound (B) having an acidic group preferably contains two or more acidic groups.
  • the resin composition of the present invention preferably further comprises a crosslinking agent (F).
  • the crosslinking agent (F) is an epoxy compound.
  • the epoxy compound is preferably an epoxy compound having an alicyclic structure.
  • the binder resin (A) is at least one polymer selected from a cyclic olefin polymer having a protic polar group, an acrylic resin, a cardo resin, a polysiloxane, and a polyimide. Is preferred.
  • the compound (D) is preferably a compound having a functional group that can further react with a protic polar group.
  • the functional group which can react with the protic polar group of the said compound (D) is an isocyanate group, a mercapto group, an epoxy group, or an amino group.
  • the content of the compound (B) is not less than the content of the compound (D).
  • substrate is provided.
  • the laminate of the present invention can be obtained by a method for producing a laminate, wherein the resin film is formed on a substrate using a resin composition.
  • the resin film may be a patterned resin film.
  • the resin film is formed on a substrate using the resin composition of the present invention, and the resin film is irradiated with actinic radiation to form a latent image in the resin film. It can be obtained by a laminate manufacturing method in which a pattern is formed, and then a latent image pattern is exposed by bringing a developer into contact with the resin film, thereby patterning the resin film.
  • a semiconductor device comprising the laminate of the present invention is provided.
  • the resin composition of the present invention is excellent in electrical characteristics, can be easily designed in the shape of a pattern, has high shape retention even after high-temperature heating, and has excellent transparency and chemical resistance. Applicable. Moreover, since the laminate of the present invention is excellent in electrical characteristics, shape retention, transparency and chemical resistance, for example, in electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices. Is a protective film for preventing deterioration and damage, a flattening film for flattening the element surface and wiring, and an electric insulating film for maintaining electrical insulation (for thin transistor type liquid crystal display elements and integrated circuit elements).
  • the laminate of the present invention is excellent in adhesion, the yield is improved by suppressing the peeling between layers in the electronic component manufacturing process, and the product including the electronic component does not move normally due to a change in use environment. Such a defect disappears. Therefore, it is possible to manufacture a product that incorporates electronic components that are inexpensive and have high performance.
  • the resin composition of the present invention comprises a binder resin (A), a compound (B) having an acidic group, an organic solvent (C), and one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom. And a compound (B) having a hydrocarbyloxy group or a hydroxy group bonded to the atom and having an acidic group is obtained from an aliphatic compound, an aromatic compound, and a heterocyclic compound.
  • the total content of the compound (B) and the compound (D) is 10 to 50 parts by weight with respect to 100 parts by weight of the binder resin (A).
  • Binder resin (A) in the present invention, is not particularly limited, but is preferably a cyclic olefin polymer having a protic polar group, an acrylic resin, a cardo resin, a polysiloxane or a polyimide, and among these, the protic polarity A cyclic olefin polymer having a group is particularly preferred.
  • These binder resins (A) may be used alone or in combination of two or more.
  • the proton polar group means a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the Periodic Table.
  • the atom belonging to group 15 or 16 of the periodic table is preferably an atom belonging to the first period or the second period of group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or A sulfur atom, particularly preferably an oxygen atom.
  • the protic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group, a secondary amino group, and a primary group.
  • a polar group having a nitrogen atom such as a secondary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable.
  • the number of protic polar groups bonded to the cyclic olefin polymer having a protic polar group is not particularly limited, and different types of protic polar groups may be included.
  • the cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond.
  • the cyclic olefin polymer may have a unit derived from a monomer other than the cyclic olefin monomer.
  • the ratio of the cyclic olefin monomer unit in the total structural units of the cyclic olefin polymer is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.
  • the protic polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer. It is desirable that it is bonded to a cyclic olefin monomer unit.
  • a cyclic olefin monomer having a protic polar group (a), a cyclic olefin having a polar group other than a protic polar group Body (b), cyclic olefin monomer (c) having no polar group, and monomer (d) other than cyclic olefin (hereinafter these monomers are simply referred to as monomers (a) to (d)). Said).
  • the monomer (d) may have a protic polar group or other polar group, or may not have a polar group at all.
  • the cyclic olefin polymer having a protic polar group is preferably composed of the monomer (a), the monomer (b) and / or the monomer (c). More preferably, it is composed of the body (a) and the monomer (b).
  • the monomer (a) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene. Ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetra Cyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 .
  • Hydroxyl-containing cyclic olefins such as 0 2,7 ] dodec-4-ene; among them, carboxy-containing cyclic olefins are preferred.
  • These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.
  • ester groups alkoxycarbonyl groups and aryloxycarbonyl groups
  • N-substituted imide group epoxy group, halogen atom, cyano group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, acryloyl group Etc.
  • an ester group, an N-substituted imide group and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.
  • the monomer (b) include the following cyclic olefins.
  • the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 3,6 .
  • dodec-4-ene 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 3,6 .
  • Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl -4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, And 3-dicarboximide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and the like.
  • Examples of cyclic olefins having a cyano group include 9-cyanotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene and the like.
  • Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and the like.
  • These cyclic olefin monomers (b) having a polar group other than the protic polar group may be used alone or in combination of two or more.
  • cyclic olefin monomer (c) having no polar group examples include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2. 2.1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene- Bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8 - diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 2,11.
  • dodec-4-ene 9-vinyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 3,9 . 0 2,10] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 3, 6. 0 2,7] dodeca-4-ene, tetracyclo [9.2.1.0 2,10.
  • cyclic olefin monomers (c) having no polar group may be used alone or in combination of two or more.
  • a specific example of the monomer (d) other than the cyclic olefin includes a chain olefin.
  • the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, ⁇ -olefins having 2 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc .; 1,4-hexadiene, 4-methyl-1 , 4-hexa
  • the cyclic olefin polymer having a protic polar group for use in the present invention is obtained by polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d), if desired. It is done.
  • the polymer obtained by polymerization may be further hydrogenated. Hydrogenated polymers are also included in the cyclic olefin polymers having protic polar groups used in the present invention.
  • the cyclic olefin polymer having a protic polar group used in the present invention introduces a protic polar group into a cyclic olefin polymer having no protic polar group by using a known modifier. It can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Further, the cyclic olefin polymer having a protic polar group may be modified using a modifying agent to further introduce a protic polar group based on the modifying agent. A polymer having no protic polar group can be obtained by polymerizing the monomers (b) to (d) in any combination.
  • a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
  • Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid.
  • Unsaturated carboxylic acids such as acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Unsatisfactory such as 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol Alcohol; and the like.
  • the modification reaction of the cyclic olefin polymer using this modifier may be carried out in accordance with a conventional method and is usually performed in the presence of a radical generator.
  • the polymerization method for polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired may be in accordance with a conventional method, for example, ring-opening polymerization method or An addition polymerization method is employed.
  • the polymerization catalyst for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more.
  • the amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably, as a molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 500,000.
  • Hydrogenation of the polymer obtained by polymerizing each monomer is usually performed using a hydrogenation catalyst.
  • a hydrogenation catalyst for example, those generally used for hydrogenation of olefin compounds can be used.
  • a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used.
  • no side reactions such as functional group modification occur, and noble metals such as rhodium and ruthenium can be selectively hydrogenated from the main chain carbon-carbon unsaturated bonds in the polymer.
  • a complex catalyst is preferable, and a nitrogen-containing heterocyclic carbene compound having a high electron donating property or a ruthenium catalyst coordinated with a phosphine is particularly preferable.
  • the hydrogenation rate of the main chain of the hydrogenated polymer is usually 90% or more, preferably 95% or more, more preferably 98% or more.
  • the binder resin (A) is particularly excellent in heat resistance and suitable.
  • the hydrogenation rate of the binder resin (A) can be measured by 1 H-NMR spectrum. For example, it can be determined as a ratio of the number of moles of hydrogenated carbon-carbon double bonds to the number of moles of carbon-carbon double bonds before hydrogenation.
  • cyclic olefin polymer having a protic polar group those having a structural unit represented by the formula (I) as shown below are particularly preferable and represented by the formula (I). What has a structural unit represented by a structural unit and Formula (II) is more suitable.
  • R 1 to R 4 each independently represents a hydrogen atom or a —X n —R ′ group
  • X is a divalent organic group; n is 0 or 1; R ′ Is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group.
  • At least one of R 1 to R 4 is a —X n —R ′ group where R ′ is a protic polar group.
  • m is an integer of 0-2.
  • R 5 to R 8 are in any combination and form a ring structure with two carbon atoms to which they are bonded, and the ring structure is an oxygen atom or a nitrogen atom as a ring constituent atom.
  • the heterocyclic ring may have a substituent.
  • k is an integer of 0-2.
  • examples of the divalent organic group represented by X include a methylene group, an ethylene group, and a carbonyl group.
  • the alkyl group which may have a substituent represented by R ′ is usually a linear or branched alkyl group having 1 to 7 carbon atoms, and examples thereof include a methyl group, an ethyl group, n -Alkyl groups such as propyl group and isopropyl group.
  • the aromatic group which may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include an aromatic group such as a phenyl group and a benzyl group.
  • substituents introduced into these alkyl groups or aromatic groups when these alkyl groups or aromatic groups have substituents include methyl, ethyl, n-propyl, isopropyl, n- And alkyl groups having 1 to 4 carbon atoms such as butyl group and isobutyl group; aryl groups having 6 to 12 carbon atoms such as phenyl group, xylyl group, tolyl group and naphthyl group;
  • Examples of the protic polar group represented by R ′ include the groups described above.
  • examples of the 3-membered heterocyclic structure formed by R 5 to R 8 together with two carbon atoms to which R 5 to R 8 are bonded include an epoxy structure.
  • Examples of the substituent introduced into the heterocyclic ring when the heterocyclic ring has a substituent include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the acrylic resin used in the present invention is not particularly limited, but a homopolymer having at least one selected from a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound as an essential component. Or a copolymer is preferable.
  • carboxylic acid having an acrylic group examples include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, and the like.
  • carboxylic acid anhydride having an acrylic group examples include maleic anhydride, citraconic anhydride, and the like.
  • epoxy group-containing acrylate compound examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, acrylate 3,4 -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, etc. It is done.
  • (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable.
  • “(meth) acryl” means either methacryl or acryl.
  • the acrylic resin is a copolymer of at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an epoxy group-containing unsaturated compound and another acrylate monomer or a copolymerizable monomer other than an acrylate. It may be a polymer.
  • acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl
  • butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.
  • the copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound.
  • vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, ⁇ -methyl styrene, butadiene, and isoprene. These compounds may be used alone or in combination of two or more.
  • the monomer polymerization method may be in accordance with a conventional method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like is employed.
  • a cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure.
  • a common cardo structure is a fluorene ring bonded to a benzene ring.
  • Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
  • the cardo resin used in the present invention is formed by polymerizing the skeleton having the cardo structure by a reaction between functional groups bonded thereto.
  • the cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.
  • cardo structure An example of a cardo structure having an epoxy glycidyl ether structure is shown in Formula (III).
  • n an integer of 0 to 10.
  • Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenolfluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
  • the cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
  • the polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.
  • the structure of the polysiloxane used in the present invention is not particularly limited, but a polysiloxane obtained by mixing and reacting one or more of organosilanes represented by the formula (IV) is preferable.
  • R 9 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, more R 9 each R 10 represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms.
  • R 10 may be the same or different, and n represents an integer of 0 to 3.
  • R 9 in the formula (IV) represents a hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, more R 9 is the same respectively It can be different.
  • these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be unsubstituted without a substituent, and are selected according to the characteristics of the composition. it can.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group.
  • alkenyl group examples include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.
  • aryl group examples include phenyl, tolyl, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl, 2- (p-hydroxyphenyl) ethyl, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.
  • R 10 is hydrogen Formula (IV), an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, even more R 10 is the same as each It may be different.
  • these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • Specific examples of the acyl group include an acetyl group.
  • aryl group examples include a phenyl group.
  • N in the formula (IV) represents an integer of 0 to 3.
  • organosilane represented by the formula (IV) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltrisilane Isopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane
  • organosilanes trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. These organosilanes may be used alone or in combination of two or more.
  • the polysiloxane in the present invention can be obtained by hydrolyzing and partially condensing the above organosilane.
  • a general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.
  • the polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react.
  • the precursor for obtaining the polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
  • the polyimide used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as ⁇ -butyrolactone and cyclopentanone.
  • the weight average molecular weight (Mw) of the binder resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10 , 000.
  • the molecular weight distribution of the binder resin (A) is a weight average molecular weight / number average molecular weight (Mw / Mn) ratio, and is usually 4 or less, preferably 3 or less, more preferably 2.5 or less.
  • the weight average molecular weight (Mw) and molecular weight distribution of the binder resin (A) can be measured using gel permeation chromatography. For example, it can be determined as a molecular weight in terms of polystyrene using a solvent such as tetrahydrofuran as an eluent.
  • the compound (B) having an acidic group is used as an essential component of the resin composition.
  • the compound (B) having an acidic group is not particularly limited as long as it has an acidic group, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound, and more preferably an aromatic compound or a heterocyclic ring.
  • a compound By using the compound as the compound (B) having an acidic group, adhesion can be further improved.
  • These compounds (B) can be used alone or in combination of two or more.
  • the number of acidic groups is not particularly limited, but those having two or more acidic groups are preferable, and those having two acidic groups are particularly preferable.
  • the acidic groups may be the same as or different from each other.
  • the acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group. It is done.
  • a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable in that the adhesion can be further improved.
  • the first dissociation constant pKa1 is defined as the acid dissociation constant.
  • BH represents an organic acid
  • B ⁇ represents a conjugate base of the organic acid.
  • the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density
  • the resin film formed from the resin composition of this invention is excellent in adhesiveness by using these acidic groups.
  • the compound (B) may have a substituent other than an acidic group.
  • substituents include hydrocarbon groups such as alkyl groups and aryl groups; halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; alkyl groups, aryl groups, and heterocyclic groups. Substituted amino groups, acylamino groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups; alkylthio groups, arylthio groups, heterocyclic thio groups; polar groups having no protons, etc. And a hydrocarbon group substituted with a polar group having no proton.
  • the compound (B) include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glyceric acid, and ethane.
  • Diacid also called “oxalic acid”
  • propanedioic acid also called “malonic acid”
  • butanedioic acid also called “succinic acid”
  • pentanedioic acid hexanedioic acid
  • adipic acid also called 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid
  • mercaptosuccinic acid dimercaptosuccinic acid, 2,3-dimercapto-1- Propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3- Butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, aliphatic compounds such as 1,5-dimercapto-3
  • the number of acidic groups is preferably two or more, and particularly preferably two preferable.
  • the compounds having two acidic groups include ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (“phthalic acid”).
  • Benzene-1,3-dicarboxylic acid also referred to as “isophthalic acid”
  • benzene-1,4-dicarboxylic acid also referred to as “terephthalic acid”
  • biphenyl-2,2′-dicarboxylic acid also referred to as “isophthalic acid”
  • the content of the compound (B) having an acidic group in the resin composition of the present invention is usually 5 to 45 parts by weight, preferably 7 to 40 parts by weight, more preferably 100 parts by weight of the binder resin (A).
  • the range is preferably 10 to 30 parts by weight. If the usage-amount of the compound (B) which has an acidic group exists in this range, the resin composition which is excellent in liquid stability can be obtained.
  • the hydrocarbyloxy group is preferably a hydrocarbyloxy group having 1 to 18 carbon atoms.
  • the compound (D) particularly preferably has a functional group capable of reacting with the protic polar group.
  • the functional group capable of reacting with the protic polar group is preferably an isocyanate group, a mercapto group, an epoxy group, or an amino group, and more preferably an epoxy group.
  • the compound (D) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimeth,
  • a silicon atom-containing compound and a titanium atom-containing compound are preferable, a silicon atom-containing compound is more preferable, and a silicon atom-containing compound having a functional group capable of reacting with a protic polar group is particularly preferable.
  • substrate can be improved more.
  • the functional group capable of reacting with the protic polar group include an amino group, a mercapto group, an isocyanate group, a glycidoxy group, an epoxy group, and a ureido group, and a glycidoxy group and an epoxy group are preferable.
  • the compound having a functional group capable of reacting with the protic polar group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, n-2- (aminoethyl) -3-aminopropyltri Methoxysilane, n-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxys
  • the content of the compound (D) in the resin composition of the present invention is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the binder resin (A). Range. If the usage-amount of a compound (D) exists in this range, since the adhesiveness of the resin film formed from a resin composition and a board
  • the total content of the compound (B) and the compound (D) is 10 to 50 parts by weight, preferably 13 to 40 parts by weight, particularly preferably 15 parts per 100 parts by weight of the binder resin (A). ⁇ 35 parts by weight.
  • the total amount is less than 10 parts by weight, the effect of improving adhesion cannot be obtained.
  • the radiation-sensitive compound (E) is added to impart photosensitivity to the resin composition.
  • the amount of film reduction during development of the coating film increases.
  • it is preferable that content of the said compound (B) is more than content of a compound (D), and content of the said compound (B) is larger than content of a compound (D). Is more preferable. When content of a compound (B) is more than content of a compound (D), it shows a high effect on adhesive improvement.
  • Organic solvent (C) used in the present invention is not particularly limited. Specific examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono t-butyl ether, propylene glycol monoethyl Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Alkylene glycol monoethers such as diethyl glycol ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether; diethylene glycol dimethyl ethylene glycol dimethyl
  • organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent (C) used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts per 100 parts by weight of the binder resin (A). The range is parts by weight.
  • the resin composition of the present invention preferably further comprises a radiation sensitive compound (E).
  • the radiation sensitive compound (E) used in the present invention is a compound capable of causing a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams.
  • the radiation sensitive compound (E) is preferably one capable of controlling the alkali solubility of the resin film formed from the resin composition.
  • Examples of the radiation sensitive compound (E) include azide compounds such as acetophenone compounds, triarylsulfonium salts, quinonediazide compounds, and the like, preferably azide compounds, and particularly preferably quinonediazide compounds.
  • quinonediazide compound for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used.
  • the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned.
  • Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1 -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like.
  • phenolic hydroxyl group examples include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
  • a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)-
  • a condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) is more preferred.
  • Photoacid generators include quinonediazide compounds, onium salts, halogenated organic compounds, ⁇ , ⁇ '-bis (sulfonyl) diazomethane compounds, ⁇ -carbonyl- ⁇ '-sulfonyldiazomethane compounds, sulfone compounds, organic acids Known compounds such as ester compounds, organic acid amide compounds, and organic acid imide compounds can be used. These radiation-sensitive compounds can be used alone or in combination of two or more.
  • the content of the radiation sensitive compound (E) in the resin composition of the present invention is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the binder resin (A).
  • the range is parts by weight.
  • a resin film made of the resin composition of the present invention is formed on an arbitrary substrate, and when the formed resin film is patterned, the resin film Among them, the difference in solubility in the developer between the radiation irradiated portion and the non-radiation irradiated portion is increased, which is preferable because patterning by development is easy and radiation sensitivity is increased.
  • Cross-linking agent (F) In this invention, it is preferable to further contain a crosslinking agent (F) as a component of a resin composition.
  • a crosslinking agent (F) one having two or more, preferably three or more functional groups capable of reacting with the binder resin (A) in the molecule is used.
  • the functional group possessed by the cross-linking agent (F) is not particularly limited as long as it can react with a functional group or an unsaturated bond in the binder resin, but a functional group capable of reacting with a protic polar group is preferable.
  • Examples of such a functional group include an amino group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and still more preferably an epoxy group.
  • crosslinking agent (F) examples include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ′′, N Melamines such as ′′-(hexaalkoxymethyl) melamine; Glycolurils such as N, N ′, N ′′, N ′ ′′-(tetraalkoxymethyl) glycoluril; Ethylene glycol di (meth) acrylate and the like Acrylate compound; hexamethylene diisocyanate polyisocyanate,
  • isocyanate compounds include the Death Module series (Desmodule BL3370, Deathmodule VPLS2253) and Clelan series (Clelan V1, Clelan VPLS2256) manufactured by Sumitomo Bayer Urethane Co., Ltd., and the Takenate series (B -815N, B-882N, B-874N), and Coronate series (Coronate L) manufactured by Nippon Polyurethane.
  • Death Module series Desmodule BL3370, Deathmodule VPLS2253
  • Clelan series Clelan V1, Clelan VPLS2256
  • Takenate series B -815N, B-882N, B-874N
  • Coronate series Coronate series manufactured by Nippon Polyurethane.
  • melamines include “Cymel 300”, “Cymel 301”, “Cymel 303”, “Cymel 350”, “Cymel 1123”, “Cymel 370”, “Cymel 771”, “Cymel 272”, “My “Coat 102", “Cymel 325", “Cymel 327”, “Cymel 703”, “Cymel 712”, “My Coat 105”, “My Coat 106", “Cymel 266”, “Cymel 267”, “Cymel 285" , “Cymel 232”, “Cymel 235”, “Cymel 236”, “Cymel 238”, “My Coat 506”, “Cymel 701”, “Cymel 272”, “Cymel 212”, “Cymel 253”, “Cymel 254” ”,“ My Coat 508 ”,“ Cymel 1128 ”,“ My Coat 130 ”, “Cymel 202”, “Cymel 207” (manufactured by Cytec Industries, Inc.
  • glycolurils include “Cymel 1170”, “Cymel 1172” (manufactured by Cytec Industries, Inc.), “Nicarac MX-270” (manufactured by Sanwa Chemical Co., Ltd.), and the like.
  • the epoxy compound examples include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.) and 2,2-bis (hydroxymethyl) 1-butanol.
  • 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group.
  • epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ⁇ -caprolactone aliphatic cyclic trifunctional epoxy resin.
  • Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP” (Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”, Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto) Yakuhin Kogyo Co., Ltd.), diglycerin polygly
  • the molecular weight of the crosslinking agent (F) is not particularly limited, but is usually 100 to 100,000, preferably 500 to 50,000, and more preferably 1,000 to 10,000.
  • a crosslinking agent can be used individually or in combination of 2 types or more, respectively.
  • the content of the crosslinking agent (F) in the resin composition of the present invention is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 100 parts by weight of the binder resin (A). It is in the range of 5 to 100 parts by weight. If the usage-amount of a crosslinking agent exists in this range, sufficient heat resistance will be acquired and it is preferable.
  • the resin composition of the present invention may be a sensitizer, a surfactant, a latent acid generator, an antioxidant, a light stabilizer, a quenching agent, if desired, as long as the effects of the present invention are not impaired.
  • Other compounding agents such as foaming agents, pigments, dyes and the like may be contained.
  • sensitizer examples include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.
  • surfactant as a component of a resin composition.
  • the surfactant is used for the purpose of preventing striation (after application stripes) and improving developability.
  • Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether.
  • Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer surfactants Agents; acrylic acid copolymer surfactants; and the like.
  • the latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention.
  • Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.
  • antioxidants there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers.
  • phenolic antioxidant 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t- Butyl-4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl -2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6- t-butylphenol), pentaerythritol tetrakis [3- (3,5-di-t-but
  • a light stabilizer as a component of the resin composition.
  • the light stabilizer may be any of benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex-based and other ultraviolet absorbers, hindered amine-based (HALS), and the like that captures radicals generated by light.
  • HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention.
  • Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
  • the preparation method of the resin composition of the present invention is not particularly limited, and each component of the resin composition of the present invention, that is, the binder resin (A), the compound having an acidic group (B), Compound (D) and organic solvent (C) having one atom selected from silicon atom, titanium atom, aluminum atom and zirconium atom, and having hydrocarbyloxy group or hydroxy group bonded to the atom, and optionally What is necessary is just to mix the other component to be used by a well-known method.
  • the mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component of the resin composition in the organic solvent (C). Thereby, the resin composition of this invention is obtained with the form of a solution or a dispersion liquid.
  • the method for dissolving or dispersing each component of the resin composition of the present invention in the organic solvent (C) may be in accordance with a conventional method. Specific examples include a method of stirring using a stirrer and a magnetic stirrer, and a method of using a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a triple roll, and the like. Further, after each component is dissolved or dispersed in the organic solvent (C), it may be filtered using, for example, a filter having a pore size of about 0.5 ⁇ m.
  • the solid content concentration when each component of the resin composition of the present invention is dissolved or dispersed in the organic solvent (C) is usually 1 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50%. % By weight. If the solid content concentration is in this range, the dissolution stability, the coating property on the substrate, the film thickness uniformity of the formed resin film, the flatness, etc. can be highly balanced.
  • Laminate The laminate of the present invention can be obtained by forming a resin film on a substrate using the resin composition of the present invention.
  • a substrate for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used.
  • a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.
  • the method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used.
  • the coating method is, for example, a method of removing a solvent by applying a resin composition on a substrate and then drying by heating.
  • Examples of the method for applying the resin composition on the substrate include various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. Can be adopted.
  • the heating and drying conditions vary depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., preferably 60 to 120 ° C., and the heating time is usually 0.5 to 90 minutes. It is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
  • the resin composition is applied on a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film. Is laminated on the substrate.
  • the heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes.
  • Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.
  • the thickness of the resin film formed on the substrate is usually 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, more preferably 0.5 to 30 ⁇ m.
  • a resin crosslinking reaction can be performed.
  • Crosslinking of the resin film formed on the substrate may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating.
  • the heating method can be performed using, for example, a hot plate or an oven.
  • the heating temperature is usually 180 to 250 ° C.
  • the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used.
  • the oven is usually run for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes.
  • Heating may be performed in an inert gas atmosphere as necessary.
  • the inert gas is not particularly limited as long as it does not contain oxygen and does not oxidize the resin film.
  • Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton.
  • nitrogen and argon are preferable, and nitrogen is particularly preferable.
  • an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.
  • the resin film may be patterned to form a patterned resin film.
  • the patterned resin film formed on the substrate for example, exposes the resin film to actinic radiation to form a latent image pattern, and then exposes the developer film to the resin film having the latent image pattern to reveal the pattern. Can be obtained.
  • a latent image pattern is formed by irradiating the resin film formed on the substrate with active radiation.
  • the actinic radiation is not particularly limited as long as it can activate the photoacid generator and change the alkali solubility of the crosslinkable composition containing the photoacid generator.
  • ultraviolet rays ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams;
  • a conventional method may be followed.
  • a method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used.
  • the active radiation it may be single wavelength light or mixed wavelength light.
  • Irradiation conditions are appropriately selected depending on the actinic radiation to be used. For example, when a light beam having a wavelength of 200 to 450 nm is used, the irradiation amount is usually 10 to 1,000 mJ / cm 2 , preferably 50 to 500 mJ / cm 2 . It is a range of cm 2 and is determined according to irradiation time and illuminance.
  • the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.
  • the latent image pattern formed on the resin film is developed and made visible.
  • a process is called “patterning”, and the patterned resin film is called “patterned resin film”.
  • an aqueous solution of an alkaline compound is usually used.
  • the alkaline compound for example, an alkali metal salt, an amine, or an ammonium salt can be used.
  • the alkaline compound may be an inorganic compound or an organic compound.
  • alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like.
  • alkaline compounds can be
  • the aqueous medium of the alkaline aqueous solution water; water-soluble organic solvents such as methanol and ethanol can be used.
  • the alkaline aqueous solution may have a surfactant added in an appropriate amount.
  • a method of bringing the developer into contact with the resin film having the latent image pattern for example, a paddle method, a spray method, a dipping method, or the like is used.
  • the development conditions may be appropriately selected.
  • the development temperature is usually in the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and the development time is usually 30 to 30 ° C. The range is 180 seconds.
  • the substrate is rinsed with a rinsing solution in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate, if necessary. Can do.
  • the remaining rinse liquid is removed with compressed air or compressed nitrogen.
  • the entire surface of the substrate having the patterned resin film can be irradiated with actinic radiation in order to deactivate the photoacid generator.
  • actinic radiation the method exemplified in the method for forming a latent image pattern can be used. You may heat a resin film simultaneously with irradiation of actinic radiation, or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.
  • the crosslinking reaction of patterned resin can be performed.
  • the crosslinking may be performed in the same manner as the above-described crosslinking of the resin film formed on the substrate.
  • the laminate of the present invention is useful as various electronic components, particularly semiconductor devices.
  • Polymerization conversion rate The polymerization conversion rate was calculated from the measured value by measuring the amount of residual monomer by gas chromatography.
  • Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) It was measured as a polystyrene equivalent value by gel permeation chromatography using tetrahydrofuran as an eluent.
  • Hydrogenation rate The hydrogenation rate was measured by 1 H-NMR, and the hydrogenated carbon-carbon double bond moles before hydrogenation relative to the carbon-carbon double bond moles before hydrogenation. The ratio was calculated from the measured value.
  • dodec-4-ene (also referred to as “tetracyclododecene”) 40 parts, 1,5-hexadiene 2.8 parts, (1,3-dimesitylimidazolidine-2-ylidene) ( Tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol ethyl methyl ether 400 part were charged into a nitrogen-substituted pressure-resistant glass reactor, and the polymerization reaction was carried out at 80 ° C. for 2 hours with stirring to obtain a ring-opening metathesis polymer 1A. A polymerization reaction solution was obtained. The polymerization conversion rate was 99.9% or more.
  • the polymer 1A had a weight average molecular weight of 3,200, a number average molecular weight of 1,900, and a molecular weight distribution of 1.68.
  • the obtained solution was taken out, the solution was filtered with a fluororesin filter having a pore size of 0.2 ⁇ m to separate activated carbon, and 476 parts of hydrogenation reaction solution containing hydride 1B of ring-opening metathesis polymer 1A. Got. Filtration could be performed without any delay.
  • the hydrogenation reaction solution containing hydride 1B obtained here had a solid content concentration of 20.6%, and the yield of hydride 1B was 98.1 parts.
  • the obtained hydride 1B had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, and a molecular weight distribution of 1.72.
  • the hydrogenation rate was 99.9%.
  • the obtained hydrogenation reaction solution of hydride 1B was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride 1C (a cyclic olefin polymer having a carboxy group as a protic polar group) was prepared. Obtained. There was no change in yield, hydride weight average molecular weight, number average molecular weight, and molecular weight distribution before and after concentration.
  • binder resin (A) 100 parts of the acrylic resin solution obtained in Production Example 1 (in terms of solid content), and as radiation sensitive compound (E), 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) (Toyo Gosei Co., Ltd., “TS200 (product name)”) 25 parts, 20 parts of 2- (carboxymethyl) benzoic acid as compound (B) having an acidic group, 92 parts of diethylene glycol ethyl methyl ether and 8 parts of N-methyl-2-pyrrolidone as the organic solvent (C), compound ( D) as 10 parts of 3-mercaptopropyltrimethoxysilane and as crosslinking agent (F) epoxidized butanetetracarboxylic acid tetrakis (3-cyclo (Xeny
  • Example 2 [Examples 2 to 7]
  • the compound (B), the compound (D), and the crosslinking agent (F) shown in Table 1 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively.
  • a resin composition was prepared in the same manner as in Example 1 except that the amount was changed to the amount shown in Table 1. Then, a laminate was obtained, and the adhesiveness of the obtained laminate was evaluated. The results are shown in Table 1.
  • Example 8 In Example 1, the cyclic olefin polymer obtained in Production Example 2 was used as the binder resin (A), and the compounds (B), (D), and crosslinking agents (F) shown in Tables 1 and 2, respectively.
  • a resin composition was prepared in the same manner as in Example 1, except that the compound (B), the compound (D), and the crosslinking agent (F) were added in the amounts shown in Tables 1 and 2. Subsequently, the laminated body was obtained and adhesiveness was evaluated about the obtained laminated body. The results are shown in Tables 1-2.
  • Example 1 the cardo resin obtained in Production Example 3 was used as the binder resin (A), and the compounds shown in Tables 2 to 3 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively.
  • a resin composition was prepared in the same manner as in Example 1 except that (B), compound (D) and crosslinking agent (F) were used, and the addition amounts thereof were as shown in Tables 2 to 3.
  • a body was obtained, and adhesion was evaluated for the obtained laminate. The results are shown in Tables 2-3.
  • Example 1 the polysiloxane obtained in Production Example 4 was used as the binder resin (A), and the compounds shown in Tables 3 to 4 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively.
  • a resin composition was prepared in the same manner as in Example 1 except that (B), compound (D) and crosslinking agent (F) were used, and the addition amounts thereof were as shown in Tables 3 to 4.
  • a body was obtained, and adhesion was evaluated for the obtained laminate. The results are shown in Tables 3-4.
  • Example 29 to 35 In Example 1, the polyimide obtained in Production Example 5 was used as the binder resin (A), and the compounds (B), the compound (D), and the crosslinking agent (F) were each of the types of compounds shown in Tables 4 to 5 ( B), a resin composition was prepared in the same manner as in Example 1 except that the compound (D) and the crosslinking agent (F) were used, and the blending amounts thereof were as shown in Tables 4 to 5. The adhesion of the obtained laminate was evaluated. The results are shown in Tables 4-5.
  • Example 36 In Example 1, as binder resin (A), compound (B), compound (D) and crosslinking agent (F), binder resins (A), compound (B) and compound ( A resin composition was prepared in the same manner as in Example 1 except that D) and the crosslinking agent (F) were used, and the blending amounts thereof were those shown in Tables 5 to 6, and then a laminate was obtained. The adhesion was evaluated for the laminated body.
  • the binder resin (A) used in Example 46 the cyclic olefin polymer having no protic polar group obtained in Production Example 6 was used. The results are shown in Tables 5-6.
  • each resin was used in the same manner as in Example 1 except that only one compound (B) and one compound (D) shown in Table 7 were used. A composition was prepared, a laminate was then obtained, and the adhesion of the obtained laminate was evaluated. The results are shown in Table 7.
  • SR-4GL polyglycerin polyglycidyl ether compound (trade name “SR-4GL”, manufactured by Sakamoto Pharmaceutical Co., Ltd.)
  • GT401 epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.)
  • Resin of Examples 1 to 46 which is at least one selected from the group and has a total content of compound (B) and compound (D) in the range of 10 to 50 with respect to 100 parts by weight of binder resin (A)
  • binder resin (A) When a resin film is formed on a substrate using the composition, the adhesion of the obtained resin film to the substrate is high.

Abstract

Disclosed is a resin composition containing (A) a binder resin, (B) a compound having an acidic group, (C) an organic solvent and (D) a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom and a zirconium atom, and a hydrocarbyloxy group or a hydroxy group bonded to the atom.  The resin composition is characterized in that the compound (B) having an acidic group is composed of at least one compound selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds, and the total amount of the compound (B) and the compound (D) is 10-50 parts by weight relative to 100 parts by weight of the binder resin (A).  Also disclosed are a laminate which is obtained by arranging a resin film composed of the resin composition on a substrate and a semiconductor device composed of the laminate.

Description

感放射線樹脂組成物、積層体及びその製造方法ならびに半導体デバイスRadiation sensitive resin composition, laminate, method for producing the same, and semiconductor device
　本発明は、樹脂組成物及びこの樹脂組成物から得られる樹脂膜を基板上に有する積層体に関し、更に詳しくは、表示素子、集積回路素子、固体撮像素子等の電子部品の製造に好適な樹脂組成物、この樹脂組成物から得られる樹脂膜を基板上に有する積層体及びその製造方法並びに半導体デバイスに関する。 The present invention relates to a resin composition and a laminate having a resin film obtained from the resin composition on a substrate, and more particularly, a resin suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. The present invention relates to a composition, a laminate having a resin film obtained from the resin composition on a substrate, a method for producing the same, and a semiconductor device.
　表示素子、集積回路素子、固体撮像素子、カラーフィルタ、薄膜トランジスタ、及びブラックマトリックス等の電子部品には、その劣化や損傷を防止するための保護膜、素子表面や配線を平坦化するための平坦化膜、及び電気絶縁性を保つための電気絶縁膜等として種々の樹脂膜が設けられている。また、薄膜トランジスタ型液晶表示素子や集積回路素子等の素子には、層状に配置される複数の配線の間を絶縁するために層間絶縁膜としての樹脂膜が設けられている。
　従来、これらの樹脂膜を形成するための樹脂材料としては、エポキシ樹脂等の熱硬化性樹脂材料が汎用されていた。しかしながら、近年の配線やデバイスの高密度化に伴い、これらの樹脂材料にも、基板との密着性が良好で低誘電性等の電気特性の優れた新しい樹脂材料が求められてきた。
　これらの要求に対応するため、例えば、特許文献１には、バインダー樹脂である環状オレフィン系重合体、感放射線化合物、有機溶剤、酸性基を有する化合物であるトリメトキシシリル安息香酸、及びケイ素原子に結合したヒドロカルビルオキシ基を有する化合物であるγ－グリシドキシプロピルトリメトキシシランを含有してなる感放射線組成物が開示されている。 For electronic parts such as display elements, integrated circuit elements, solid-state imaging elements, color filters, thin film transistors, and black matrices, protective films to prevent their deterioration and damage, flattening to flatten the element surface and wiring Various resin films are provided as a film and an electric insulating film for maintaining electric insulation. In addition, a resin film as an interlayer insulating film is provided in an element such as a thin film transistor type liquid crystal display element or an integrated circuit element in order to insulate a plurality of wirings arranged in layers.
Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. However, with recent increases in the density of wiring and devices, new resin materials having excellent electrical properties such as good adhesion to the substrate and low dielectric properties have been demanded for these resin materials.
In order to meet these requirements, for example, Patent Document 1 includes a cyclic olefin polymer as a binder resin, a radiation-sensitive compound, an organic solvent, trimethoxysilylbenzoic acid as a compound having an acidic group, and a silicon atom. A radiation-sensitive composition comprising γ-glycidoxypropyltrimethoxysilane, which is a compound having a bound hydrocarbyloxy group, is disclosed.
　特許文献２には、バインダー樹脂である式（１）で表わされる有機絶縁高分子、感放射線化合物である光酸発生剤、有機溶剤、２つの酸性基を有する化合物であるフタル酸を含有してなる感放射線組成物が開示されている。特許文献２によれば、前記感放射線組成物は微細パターン形成を可能としながら電気特性の向上が図れると記載されている。
Figure JPOXMLDOC01-appb-C000001
 Patent Document 2 contains an organic insulating polymer represented by Formula (1) as a binder resin, a photoacid generator as a radiation-sensitive compound, an organic solvent, and phthalic acid as a compound having two acidic groups. A radiation sensitive composition is disclosed. According to Patent Document 2, it is described that the radiation-sensitive composition can improve electrical characteristics while enabling fine pattern formation.
Figure JPOXMLDOC01-appb-C000001
特開２００５－２９２２７７号公報JP 2005-292277 A 特開２００５－１７１２５９号公報（米国特許出願公開第２００５／１２７３５５号明細書）Japanese Patent Laying-Open No. 2005-171259 (US Patent Application Publication No. 2005/127355)
　本発明者らの検討によれば、特許文献１に記載の感放射線組成物は、実用上接着助剤を配合するが、それでも基板との密着性が十分でないこと、特許文献２に記載の感放射線組成物も基板との密着性が十分でなく、さらなる改良が必要であることがわかった。
　従って、本発明の目的は、耐熱性、耐溶剤性、表面硬度、絶縁性、平坦性、透明性、耐薬品性及び低誘電性等に優れ、更に、密着性が改良された樹脂組成物を提供することにある。
　更に本発明の他の目的は、この樹脂組成物を用いてなる樹脂膜を基板上に形成した積層体、及びこの積層体の製造方法を提供することにある。 According to the study by the present inventors, the radiation-sensitive composition described in Patent Document 1 contains an adhesion aid in practice, but still has insufficient adhesion to the substrate, and the sensitivity described in Patent Document 2. It has been found that the radiation composition also has insufficient adhesion to the substrate, and further improvement is necessary.
Accordingly, an object of the present invention is to provide a resin composition that is excellent in heat resistance, solvent resistance, surface hardness, insulation, flatness, transparency, chemical resistance, low dielectric property, etc., and has improved adhesion. It is to provide.
Furthermore, the other object of this invention is to provide the laminated body which formed the resin film which uses this resin composition on a board | substrate, and the manufacturing method of this laminated body.
　本発明者らは、上記の目的を達成すべく鋭意研究を重ねた結果、バインダー樹脂（Ａ）に、酸性基を有する化合物（Ｂ）、有機溶媒（Ｃ）、並びにケイ素原子、チタン原子、アルミニウム原子、及びジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を組み合わせてなり、前記酸性基を有する化合物（Ｂ）が、脂肪族化合物、芳香族化合物、及び複素環化合物からなる群より選ばれた少なくとも１種以上であり、前記化合物（Ｂ）と前記化合物（Ｄ）の合計含有量が前記バインダー樹脂（Ａ）１００重量部に対して特定量の範囲である樹脂組成物を用いればよいことを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the binder resin (A) has a compound (B) having an acidic group, an organic solvent (C), a silicon atom, a titanium atom, and aluminum. A compound (B) having an acidic group and a compound (D) having one atom selected from an atom and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom, It is at least one selected from the group consisting of aliphatic compounds, aromatic compounds, and heterocyclic compounds, and the total content of the compound (B) and the compound (D) is 100 weights of the binder resin (A). It has been found that a resin composition in a specific amount range with respect to the part may be used, and the present invention has been completed based on this finding.
　かくして、本発明によれば、バインダー樹脂（Ａ）、酸性基を有する化合物（Ｂ）、有機溶媒（Ｃ）、並びにケイ素原子、チタン原子、アルミニウム原子、及びジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を含有してなり、酸性基を有する化合物（Ｃ）が、脂肪族化合物、芳香族化合物、及び複素環化合物からなる群より選ばれた少なくとも１種であり、化合物（Ｂ）と化合物（Ｄ）の含有量合計が樹脂１００重量部に対して１０～５０重量部であることを特徴とする樹脂組成物が提供される。 Thus, according to the present invention, the binder resin (A), the compound (B) having an acidic group, the organic solvent (C), and one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom A compound (D) having a hydrocarbyloxy group or a hydroxy group bonded to the atom, and the compound (C) having an acidic group is an aliphatic compound, an aromatic compound, and a heterocyclic compound. A resin composition characterized in that it is at least one selected from the group consisting of 10 to 50 parts by weight of the total content of compound (B) and compound (D) with respect to 100 parts by weight of resin. Is done.
　本発明の樹脂組成物において、感放射線化合物（Ｅ）をさらに含有してなることが好ましい。 The resin composition of the present invention preferably further comprises a radiation sensitive compound (E).
　本発明の樹脂組成物において、前記酸性基を有する化合物（Ｂ）の酸性基が、カルボキシ基、チオール基、またはカルボキシメチレンチオ基であることが好ましい。 In the resin composition of the present invention, the acidic group of the compound (B) having an acidic group is preferably a carboxy group, a thiol group, or a carboxymethylenethio group.
　本発明の樹脂組成物において、前記酸性基を有する化合物（Ｂ）の、酸性基の酸解離定数ｐＫａ（酸性基が２つ以上ある場合は第一酸解離定数ｐＫａ１）が３．５以上５．０以下の範囲にあることが好ましい。
　本発明の樹脂組成物において、前記酸性基を有する化合物（Ｂ）は、酸性基を２つ以上含有することが好ましい。 In the resin composition of the present invention, the acid group acid dissociation constant pKa (the first acid dissociation constant pKa1 when there are two or more acidic groups) of the compound (B) having an acidic group is 3.5 or more and 5. It is preferably in the range of 0 or less.
In the resin composition of the present invention, the compound (B) having an acidic group preferably contains two or more acidic groups.
　本発明の樹脂組成物において、架橋剤（Ｆ）をさらに含有してなるものであることが好ましい。 The resin composition of the present invention preferably further comprises a crosslinking agent (F).
　本発明の樹脂組成物において、前記架橋剤（Ｆ）が、エポキシ化合物であることが好ましい。 In the resin composition of the present invention, it is preferable that the crosslinking agent (F) is an epoxy compound.
　本発明の樹脂組成物において、前記エポキシ化合物が、脂環構造を有するエポキシ化合物であることが好ましい。 In the resin composition of the present invention, the epoxy compound is preferably an epoxy compound having an alicyclic structure.
　本発明の樹脂組成物において、前記バインダー樹脂（Ａ）が、プロトン性極性基を有する環状オレフィン重合体、アクリル樹脂、カルド樹脂、ポリシロキサン、及びポリイミドから選ばれる１種以上の重合体であることが好ましい。 In the resin composition of the present invention, the binder resin (A) is at least one polymer selected from a cyclic olefin polymer having a protic polar group, an acrylic resin, a cardo resin, a polysiloxane, and a polyimide. Is preferred.
　本発明の樹脂組成物において、前記化合物（Ｄ）が、更にプロトン性極性基と反応し得る官能基を有する化合物であることが好ましい。また、前記化合物（Ｄ）のプロトン性極性基と反応し得る官能基が、イソシアネート基、メルカプト基、エポキシ基、又はアミノ基であることが好ましい。 In the resin composition of the present invention, the compound (D) is preferably a compound having a functional group that can further react with a protic polar group. Moreover, it is preferable that the functional group which can react with the protic polar group of the said compound (D) is an isocyanate group, a mercapto group, an epoxy group, or an amino group.
　また、本発明の樹脂組成物において、前記化合物（Ｂ）の含有量が前記化合物（Ｄ）の含有量以上であることが好ましい。 In the resin composition of the present invention, it is preferable that the content of the compound (B) is not less than the content of the compound (D).
　本発明によれば、上記本発明の樹脂組成物からなる樹脂膜を基板上に積層してなる積層体が提供される。
　上記本発明の積層体は、樹脂組成物を用いて、前記樹脂膜を基板上に形成することを特徴とする積層体の製造方法によって得ることができる。
　上記本発明の積層体の製造方法において、前記樹脂膜を基板上に形成した後、前記樹脂膜を形成する樹脂を架橋する工程を有することが好ましい。 According to this invention, the laminated body formed by laminating | stacking the resin film which consists of a resin composition of the said invention on a board | substrate is provided.
The laminate of the present invention can be obtained by a method for producing a laminate, wherein the resin film is formed on a substrate using a resin composition.
In the manufacturing method of the laminated body of the present invention, it is preferable to have a step of crosslinking the resin forming the resin film after the resin film is formed on the substrate.
　上記本発明の積層体において、前記樹脂膜がパターン化樹脂膜であってもよい。
　前記樹脂膜がパターン化樹脂膜である積層体は、本発明の樹脂組成物を用いて前記樹脂膜を基板上に形成し、前記樹脂膜に活性放射線を照射して前記樹脂膜中に潜像パターンを形成し、次いで前記樹脂膜に現像液を接触させることにより潜像パターンを顕在化させて、前記樹脂膜をパターン化する積層体の製造方法によって得ることができる。
　上記本発明のパターン化樹脂膜を有する積層体の製造方法において、基板上に前記パターン化樹脂膜を形成した後に、前記パターン化樹脂膜を形成する樹脂の架橋反応を行なう工程を有することが好ましい。 In the laminate of the present invention, the resin film may be a patterned resin film.
In the laminate in which the resin film is a patterned resin film, the resin film is formed on a substrate using the resin composition of the present invention, and the resin film is irradiated with actinic radiation to form a latent image in the resin film. It can be obtained by a laminate manufacturing method in which a pattern is formed, and then a latent image pattern is exposed by bringing a developer into contact with the resin film, thereby patterning the resin film.
In the method for producing a laminate having the patterned resin film according to the present invention, it is preferable to include a step of performing a crosslinking reaction of the resin for forming the patterned resin film after the patterned resin film is formed on the substrate. .
　更に本発明によれば、上記本発明の積層体からなる半導体デバイスが提供される。 Furthermore, according to the present invention, a semiconductor device comprising the laminate of the present invention is provided.
　本発明の樹脂組成物は、電気特性に優れ、パターンの形状の設計が容易であり、また、高温加熱後も、形状保持性が高く、透明性及び耐薬品性に優れることから様々な用途に適用できる。
　また、本発明の積層体は、電気特性、形状保持性、透明性及び耐薬品性に優れることから、例えば、表示素子、集積回路素子、固体撮像素子、カラーフィルター、ブラックマトリックス等の電子部品においては、その劣化や損傷を防止するための保護膜、素子表面や配線を平坦化するための平坦化膜、電気絶縁性を保つための電気絶縁膜（薄型トランジスタ型液晶表示素子や集積回路素子の電気絶縁膜である層間絶縁膜やソルダーレジスト膜等を含む）、マイクロレンズ、スペーサ等の電子部品用材料として好適である。
　本発明の積層体は、密着性に優れているので、電子部品製造工程における層間の剥がれを抑えられることにより歩留まりが向上し、また、電子部品を含む製品が使用環境の変化により正常に動かなくなるような不良がなくなる。従って、安価で性能の良い電子部品を内蔵する製品を作製することが可能になる。 The resin composition of the present invention is excellent in electrical characteristics, can be easily designed in the shape of a pattern, has high shape retention even after high-temperature heating, and has excellent transparency and chemical resistance. Applicable.
Moreover, since the laminate of the present invention is excellent in electrical characteristics, shape retention, transparency and chemical resistance, for example, in electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices. Is a protective film for preventing deterioration and damage, a flattening film for flattening the element surface and wiring, and an electric insulating film for maintaining electrical insulation (for thin transistor type liquid crystal display elements and integrated circuit elements). It is suitable as a material for electronic parts such as an interlayer insulating film which is an electric insulating film, a solder resist film, etc.), a microlens, a spacer and the like.
Since the laminate of the present invention is excellent in adhesion, the yield is improved by suppressing the peeling between layers in the electronic component manufacturing process, and the product including the electronic component does not move normally due to a change in use environment. Such a defect disappears. Therefore, it is possible to manufacture a product that incorporates electronic components that are inexpensive and have high performance.
　本発明の樹脂組成物は、バインダー樹脂（Ａ）、酸性基を有する化合物（Ｂ）、有機溶媒（Ｃ）、並びにケイ素原子、チタン原子、アルミニウム原子、及びジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を含有してなり、酸性基を有する化合物（Ｂ）が、脂肪族化合物、芳香族化合物、及び複素環化合物からなる群より選ばれた少なくとも１種であり、化合物（Ｂ）と化合物（Ｄ）の合計含有量が、バインダー樹脂（Ａ）１００重量部に対して１０～５０重量部である。 The resin composition of the present invention comprises a binder resin (A), a compound (B) having an acidic group, an organic solvent (C), and one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom. And a compound (B) having a hydrocarbyloxy group or a hydroxy group bonded to the atom and having an acidic group is obtained from an aliphatic compound, an aromatic compound, and a heterocyclic compound. The total content of the compound (B) and the compound (D) is 10 to 50 parts by weight with respect to 100 parts by weight of the binder resin (A).
　バインダー樹脂（Ａ）
　本発明において、バインダー樹脂（Ａ）は、特に限定されないが、プロトン性極性基を有する環状オレフィン重合体、アクリル樹脂、カルド樹脂、ポリシロキサン又はポリイミドであることが好ましく、これらの中でも、プロトン性極性基を有する環状オレフィン重合体が特に好ましい。
　これらのバインダー樹脂（Ａ）は、それぞれ単独で用いてもよく、又は２種以上を併用してもよい。 Binder resin (A)
In the present invention, the binder resin (A) is not particularly limited, but is preferably a cyclic olefin polymer having a protic polar group, an acrylic resin, a cardo resin, a polysiloxane or a polyimide, and among these, the protic polarity A cyclic olefin polymer having a group is particularly preferred.
These binder resins (A) may be used alone or in combination of two or more.
　プロトン極性基とは、周期律表第１５族又は第１６族に属する原子に水素原子が直接結合している原子を含む基をいう。周期律表第１５族又は第１６族に属する原子は、好ましくは周期律表第１５族又は第１６族の第１周期又は第２周期に属する原子であり、より好ましくは酸素原子、窒素原子又は硫黄原子であり、特に好ましくは酸素原子である。 The proton polar group means a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the Periodic Table. The atom belonging to group 15 or 16 of the periodic table is preferably an atom belonging to the first period or the second period of group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or A sulfur atom, particularly preferably an oxygen atom.
　プロトン性極性基の具体例としては、水酸基、カルボキシ基（ヒドロキシカルボニル基）、スルホン酸基、リン酸基等の酸素原子を有する極性基；第一級アミノ基、第二級アミノ基、第一級アミド基、第二級アミド基（イミド基）等の窒素原子を有する極性基；チオール基等の硫黄原子を有する極性基；等が挙げられる。これらの中でも、酸素原子を有するものが好ましく、より好ましくはカルボキシ基である。
　本発明において、プロトン性極性基を有する環状オレフィン重合体に結合しているプロトン性極性基の数に特に限定はなく、また、相異なる種類のプロトン性極性基が含まれていてもよい。 Specific examples of the protic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group, a secondary amino group, and a primary group. A polar group having a nitrogen atom such as a secondary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable.
In the present invention, the number of protic polar groups bonded to the cyclic olefin polymer having a protic polar group is not particularly limited, and different types of protic polar groups may be included.
　本発明において環状オレフィン重合体とは、環状構造（脂環又は芳香環）と炭素－炭素二重結合とを有する環状オレフィン単量体の、単独重合体又は共重合体である。環状オレフィン重合体は、環状オレフィン単量体以外の単量体から導かれる単位を有していてもよい。
　環状オレフィン重合体の全構造単位中、環状オレフィン単量体単位の割合は、通常、３０～１００重量％、好ましくは５０～１００重量％、より好ましくは７０～１００重量％である。 In the present invention, the cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have a unit derived from a monomer other than the cyclic olefin monomer.
The ratio of the cyclic olefin monomer unit in the total structural units of the cyclic olefin polymer is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.
　プロトン性極性基を有する環状オレフィン重合体において、プロトン性極性基は、環状オレフィン単量体単位に結合していても、環状オレフィン単量体以外の単量体単位に結合していてもよいが、環状オレフィン単量体単位に結合しているのが望ましい。 In the cyclic olefin polymer having a protic polar group, the protic polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer. It is desirable that it is bonded to a cyclic olefin monomer unit.
　プロトン性極性基を有する環状オレフィン重合体を構成するための単量体としては、プロトン性極性基を有する環状オレフィン単量体（ａ）、プロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ）、極性基を持たない環状オレフィン単量体（ｃ）、及び環状オレフィン以外の単量体（ｄ）（これらの単量体を以下、単に単量体（ａ）～（ｄ）という。）が挙げられる。ここで、単量体（ｄ）は、プロトン性極性基又はこれ以外の極性基を有していてもよく、極性基を全く有していなくてもよい。
　本発明において、プロトン性極性基を有する環状オレフィン重合体は、単量体（ａ）と、単量体（ｂ）及び／又は単量体（ｃ）とから構成されることが好ましく、単量体（ａ）と単量体（ｂ）とから構成されることが更に好ましい。 As monomers for constituting a cyclic olefin polymer having a protic polar group, a cyclic olefin monomer having a protic polar group (a), a cyclic olefin having a polar group other than a protic polar group Body (b), cyclic olefin monomer (c) having no polar group, and monomer (d) other than cyclic olefin (hereinafter these monomers are simply referred to as monomers (a) to (d)). Said). Here, the monomer (d) may have a protic polar group or other polar group, or may not have a polar group at all.
In the present invention, the cyclic olefin polymer having a protic polar group is preferably composed of the monomer (a), the monomer (b) and / or the monomer (c). More preferably, it is composed of the body (a) and the monomer (b).
　単量体（ａ）の具体例としては、５－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－メチル－５－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシメチル－５－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、９－ヒドロキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－ヒドロキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９，１０－ジヒドロキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン等のカルボキシ基含有環状オレフィン；５－（４－ヒドロキシフェニル）ビシクロ［２．２．１］ヘプト－２－エン、５－メチル－５－（４－ヒドロキシフェニル）ビシクロ［２．２．１］ヘプト－２－エン、９－（４－ヒドロキシフェニル）テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－（４－ヒドロキシフェニル）テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン等の水酸基含有環状オレフィン；等が挙げられ、中でもカルボキシ基含有環状オレフィンが好ましい。これらのプロトン性極性基を有する環状オレフィン単量体（ａ）は、それぞれ単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the monomer (a) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene. Ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetra Cyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 3,6 . Carboxy group-containing cyclic olefins such as 0 2,7 ] dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 3,6 . Hydroxyl-containing cyclic olefins such as 0 2,7 ] dodec-4-ene; among them, carboxy-containing cyclic olefins are preferred. These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.
　プロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ）が有する、プロトン性極性基以外の極性基の具体例としては、エステル基（アルコキシカルボニル基及びアリーロキシカルボニル基を総称していう。）、Ｎ－置換イミド基、エポキシ基、ハロゲン原子、シアノ基、カルボニルオキシカルボニル基（ジカルボン酸の酸無水物残基）、アルコキシ基、カルボニル基、第三級アミノ基、スルホン基、アクリロイル基等が挙げられる。中でも、エステル基、Ｎ－置換イミド基及びシアノ基が好ましく、エステル基及びＮ－置換イミド基がより好ましく、Ｎ－置換イミド基が特に好ましい。 Specific examples of polar groups other than protic polar groups possessed by the cyclic olefin monomer (b) having polar groups other than protic polar groups are generically referred to as ester groups (alkoxycarbonyl groups and aryloxycarbonyl groups). .), N-substituted imide group, epoxy group, halogen atom, cyano group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, acryloyl group Etc. Among them, an ester group, an N-substituted imide group and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.
　単量体（ｂ）の具体例としては、以下のような環状オレフィンが挙げられる。
　エステル基を有する環状オレフィンとしては、例えば、５－アセトキシビシクロ［２．２．１］ヘプト－２－エン、５－メトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－メチル－５－メトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、９－アセトキシテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－エトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－ｎ－プロポキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－イソプロポキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－ｎ－ブトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－メトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－エトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－ｎ－プロポキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－イソプロポキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－ｎ－ブトキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－（２，２，２－トリフルオロエトキシカルボニル）テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－（２，２，２－トリフルオロエトキシカルボニル）テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン等が挙げられる。 Specific examples of the monomer (b) include the following cyclic olefins.
Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and the like.
　Ｎ－置換イミド基を有する環状オレフィンとしては、例えば、Ｎ－フェニルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルヘキシル）－１－イソプロピル－４－メチルビシクロ［２．２．２］オクト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－［（２－エチルブトキシ）エトキシプロピル］－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド等が挙げられる。
　シアノ基を有する環状オレフィンとしては、例えば、９－シアノテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－シアノテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、５－シアノビシクロ［２．２．１］ヘプト－２－エン等が挙げられる。
　ハロゲン原子を有する環状オレフィンとしては、例えば、９－クロロテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチル－９－クロロテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン等が挙げられる。
　これらのプロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ）は、それぞれ単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl -4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, And 3-dicarboximide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and the like.
Examples of cyclic olefins having a cyano group include 9-cyanotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene and the like.
Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and the like.
These cyclic olefin monomers (b) having a polar group other than the protic polar group may be used alone or in combination of two or more.
　極性基を一切持たない環状オレフィン単量体（ｃ）の具体例としては、ビシクロ［２．２．１］ヘプト－２－エン（「ノルボルネン」ともいう。）、５－エチル－ビシクロ［２．２．１］ヘプト－２－エン、５－ブチル－ビシクロ［２．２．１］ヘプト－２－エン、５－エチリデン－ビシクロ［２．２．１］ヘプト－２－エン、５－メチリデン－ビシクロ［２．２．１］ヘプト－２－エン、５－ビニル－ビシクロ［２．２．１］ヘプト－２－エン、トリシクロ［５．２．１．０２，６］デカ－３，８－ジエン（慣用名：ジシクロペンタジエン）、テトラシクロ［１０．２．１．０２，１１．０４，９］ペンタデカ－４，６，８，１３－テトラエン、テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン（「テトラシクロドデセン」ともいう。）、９－メチル－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－エチル－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－メチリデン－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－エチリデン－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－ビニル－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、９－プロペニル－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、ペンタシクロ［９．２．１．１３，９．０２，１０］ペンタデカ－５，１２－ジエン、シクロペンテン、シクロペンタジエン、９－フェニル－テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン、テトラシクロ［９．２．１．０２，１０．０３，８］テトラデカ－３，５，７，１２－テトラエン、ペンタシクロ［９．２．１．１３，９．０２，１０］ペンタデカ－１２－エン等が挙げられる。
　これらの極性基を一切持たない環状オレフィン単量体（ｃ）は、それぞれ単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2. 2.1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene- Bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8 - diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 2,11. 0 4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 3,9 . 0 2,10] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 3, 6. 0 2,7] dodeca-4-ene, tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 3,9 . 0 2,10] pentadeca-12-ene, and the like.
These cyclic olefin monomers (c) having no polar group may be used alone or in combination of two or more.
　環状オレフィン以外の単量体（ｄ）の具体例としては、鎖状オレフィンが挙げられる。鎖状オレフィンとしては、例えば、エチレン；プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセン等の炭素数２～２０のα－オレフィン；１，４－ヘキサジエン、４－メチル－１，４－ヘキサジエン、５－メチル－１，４－ヘキサジエン、１，７－オクタジエン等の非共役ジエン；等が挙げられる。
　これらの環状オレフィン以外の単量体（ｄ）は、それぞれ単独で又は２種以上を組み合わせて用いることができる。 A specific example of the monomer (d) other than the cyclic olefin includes a chain olefin. Examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, Α-olefins having 2 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc .; 1,4-hexadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and the like.
Monomers (d) other than these cyclic olefins can be used alone or in combination of two or more.
　本発明に使用するプロトン性極性基を有する環状オレフィン重合体は、単量体（ａ）を、所望により単量体（ｂ）～（ｄ）から選ばれる単量体と共に、重合することにより得られる。重合により得られた重合体を更に水素化してもよい。水素添加された重合体も、本発明に使用する、プロトン性極性基を有する環状オレフィン重合体に包含される。 The cyclic olefin polymer having a protic polar group for use in the present invention is obtained by polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d), if desired. It is done. The polymer obtained by polymerization may be further hydrogenated. Hydrogenated polymers are also included in the cyclic olefin polymers having protic polar groups used in the present invention.
　また、本発明で使用するプロトン性極性基を有する環状オレフィン重合体は、プロトン性極性基を有しない環状オレフィン重合体に、公知の変性剤を利用してプロトン性極性基を導入し、所望により水素添加を行なう方法によっても得ることができる。水素添加は、プロトン性極性基導入前の重合体について行なってもよい。また、プロトン性極性基を有する環状オレフィン重合体に、変性剤を利用して変性を行って、変性剤に基づくプロトン性極性基を更に導入してもよい。
　プロトン性極性基を有しない重合体は、前記単量体（ｂ）～（ｄ）を任意に組み合わせて重合することによって得ることができる。 In addition, the cyclic olefin polymer having a protic polar group used in the present invention introduces a protic polar group into a cyclic olefin polymer having no protic polar group by using a known modifier. It can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Further, the cyclic olefin polymer having a protic polar group may be modified using a modifying agent to further introduce a protic polar group based on the modifying agent.
A polymer having no protic polar group can be obtained by polymerizing the monomers (b) to (d) in any combination.
　プロトン性極性基を導入するための変性剤としては、通常、一分子内にプロトン性極性基と反応性の炭素－炭素不飽和結合とを有する化合物が用いられる。
　このような化合物の具体例としては、アクリル酸、メタクリル酸、アンゲリカ酸、チグリン酸、オレイン酸、エライジン酸、エルカ酸、ブラシジン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、アトロパ酸、ケイ皮酸等の不飽和カルボン酸；アリルアルコール、メチルビニルメタノール、クロチルアルコール、メタリルアルコール、１－フェニルエテン－１－オール、２－プロペン－１－オール、３－ブテン－１－オール、３－ブテン－２－オール、３－メチル－３－ブテン－１－オール、３－メチル－２－ブテン－１－オール、２－メチル－３－ブテン－２－オール、２－メチル－３－ブテン－１－オール、４－ペンテン－１－オール、４－メチル－４－ぺンテン－１－オール、２－ヘキセン－１－オール等の不飽和アルコール；等が挙げられる。
　この変性剤を用いる環状オレフィン重合体の変性反応は、常法に従えばよく、通常、ラジカル発生剤の存在下で行われる。 As the modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Unsatisfactory such as 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol Alcohol; and the like.
The modification reaction of the cyclic olefin polymer using this modifier may be carried out in accordance with a conventional method and is usually performed in the presence of a radical generator.
　単量体（ａ）を、所望により単量体（ｂ）～（ｄ）から選ばれる単量体と共に、重合するための重合方法は、常法に従えばよく、例えば、開環重合法や付加重合法が採用される。
　重合触媒としては、例えば、モリブデン、ルテニウム、オスミウム等の金属錯体が好適に用いられる。これらの重合触媒は、それぞれ単独で又は２種以上を組み合わせて用いることができる。重合触媒の量は、重合触媒中の金属化合物：環状オレフィンのモル比で、通常、１：１００～１：２，０００，０００、好ましくは１：５００～１：１，０００，０００、より好ましくは１：１，０００～１：５００，０００の範囲である。 The polymerization method for polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired may be in accordance with a conventional method, for example, ring-opening polymerization method or An addition polymerization method is employed.
As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably, as a molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 500,000.
　各単量体を重合して得られた重合体の水素添加は、通常、水素添加触媒を用いて行われる。
　水素添加触媒としては、例えば、オレフィン化合物の水素添加に際して一般的に使用されているものを用いることができる。具体的には、チーグラータイプの均一系触媒、貴金属錯体触媒、及び担持型貴金属系触媒等が利用できる。
　これらの水素添加触媒のうち、官能基が変性する等の副反応が起きず、重合体中の主鎖の炭素－炭素不飽和結合を選択的に水素添加できる点から、ロジウム、ルテニウム等の貴金属錯体触媒が好ましく、電子供与性の高い含窒素複素環式カルベン化合物又はホスフィン類が配位したルテニウム触媒が特に好ましい。 Hydrogenation of the polymer obtained by polymerizing each monomer is usually performed using a hydrogenation catalyst.
As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used.
Among these hydrogenation catalysts, no side reactions such as functional group modification occur, and noble metals such as rhodium and ruthenium can be selectively hydrogenated from the main chain carbon-carbon unsaturated bonds in the polymer. A complex catalyst is preferable, and a nitrogen-containing heterocyclic carbene compound having a high electron donating property or a ruthenium catalyst coordinated with a phosphine is particularly preferable.
　水素添加された重合体の主鎖の水素化率は、通常、９０％以上、好ましくは９５％以上、より好ましくは９８％以上である。水素化率がこの範囲にある時に、バインダー樹脂（Ａ）は、特に耐熱性に優れ好適である。
　バインダー樹脂（Ａ）の水素化率は、１Ｈ－ＮＭＲスペクトルにより、測定することができる。例えば、水素化された炭素－炭素二重結合モル数の、水素添加前の炭素－炭素二重結合モル数に対する割合として求めることができる。 The hydrogenation rate of the main chain of the hydrogenated polymer is usually 90% or more, preferably 95% or more, more preferably 98% or more. When the hydrogenation rate is within this range, the binder resin (A) is particularly excellent in heat resistance and suitable.
The hydrogenation rate of the binder resin (A) can be measured by 1 H-NMR spectrum. For example, it can be determined as a ratio of the number of moles of hydrogenated carbon-carbon double bonds to the number of moles of carbon-carbon double bonds before hydrogenation.
　本発明においてプロトン性極性基を有する環状オレフィン重合体としては、特に、以下に示すような、式（Ｉ）で表される構造単位を有するものが好適であり、式（Ｉ）で表される構造単位及び式（ＩＩ）で表される構造単位を有するものがより好適である。 In the present invention, as the cyclic olefin polymer having a protic polar group, those having a structural unit represented by the formula (I) as shown below are particularly preferable and represented by the formula (I). What has a structural unit represented by a structural unit and Formula (II) is more suitable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
〔式（Ｉ）中、Ｒ１～Ｒ４は、それぞれ独立して、水素原子又は－Ｘｎ－Ｒ’基（Ｘは二価の有機基であり；ｎは０又は１であり；Ｒ’は、置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族基、又はプロトン性極性基である。）である。Ｒ１～Ｒ４のうち少なくとも１つは、Ｒ’がプロトン性極性基である－Ｘｎ－Ｒ’基である。ｍは０～２の整数である。〕 [In the formula (I), R 1 to R 4 each independently represents a hydrogen atom or a —X n —R ′ group (X is a divalent organic group; n is 0 or 1; R ′ Is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group. At least one of R 1 to R 4 is a —X n —R ′ group where R ′ is a protic polar group. m is an integer of 0-2. ]
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式（ＩＩ）中、Ｒ５～Ｒ８は、任意の組み合わせで、それらが結合している２つの炭素原子と共に環構造を形成し、該環構造は、環構成原子として酸素原子又は窒素原子を含む、３～５員の複素環構造である。また、該複素環は置換基を有していてもよい。ｋは０～２の整数である。〕 [In the formula (II), R 5 to R 8 are in any combination and form a ring structure with two carbon atoms to which they are bonded, and the ring structure is an oxygen atom or a nitrogen atom as a ring constituent atom. A 3- to 5-membered heterocyclic structure. In addition, the heterocyclic ring may have a substituent. k is an integer of 0-2. ]
　一般式（Ｉ）において、Ｘで示される二価の有機基の例としては、メチレン基、エチレン基及びカルボニル基等が挙げられる。
　Ｒ’で示される、置換基を有していてもよいアルキル基は、通常、直鎖又は分岐鎖の炭素数１～７のアルキル基であり、その例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等のアルキル基が挙げられる。置換基を有していてもよい芳香族基は、通常、炭素数６～１０の芳香族基であり、その例としては、フェニル基、ベンジル基等の芳香族基が挙げられる。これらのアルキル基や芳香族基が置換基を有する場合における、これらアルキル基や芳香族基に導入される置換基の例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等の炭素数１～４のアルキル基；フェニル基、キシリル基、トリル基、ナフチル基等の炭素数６～１２のアリール基；等が挙げられる。
　Ｒ’で示されるプロトン性極性基としては、上述したような基が挙げられる。 In the general formula (I), examples of the divalent organic group represented by X include a methylene group, an ethylene group, and a carbonyl group.
The alkyl group which may have a substituent represented by R ′ is usually a linear or branched alkyl group having 1 to 7 carbon atoms, and examples thereof include a methyl group, an ethyl group, n -Alkyl groups such as propyl group and isopropyl group. The aromatic group which may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include an aromatic group such as a phenyl group and a benzyl group. Examples of substituents introduced into these alkyl groups or aromatic groups when these alkyl groups or aromatic groups have substituents include methyl, ethyl, n-propyl, isopropyl, n- And alkyl groups having 1 to 4 carbon atoms such as butyl group and isobutyl group; aryl groups having 6 to 12 carbon atoms such as phenyl group, xylyl group, tolyl group and naphthyl group;
Examples of the protic polar group represented by R ′ include the groups described above.
　一般式（ＩＩ）において、Ｒ５～Ｒ８が、任意の組み合わせで、それらが結合している２つの炭素原子と共に形成する３員複素環構造としては、エポキシ構造等が挙げられる。また、同じく５員複素環構造の例としては、ジカルボン酸無水物構造〔－Ｃ（＝Ｏ）－Ｏ－Ｃ（＝Ｏ）－〕、ジカルボキシイミド構造〔－Ｃ（＝Ｏ）－Ｎ－Ｃ（＝Ｏ）－〕等が挙げられる。当該複素環が置換基を有する場合における、複素環に導入される置換基の例としては、フェニル基、ナフチル基、アントラセニル基等が挙げられる。 In the general formula (II), examples of the 3-membered heterocyclic structure formed by R 5 to R 8 together with two carbon atoms to which R 5 to R 8 are bonded include an epoxy structure. Similarly, examples of 5-membered heterocyclic structures include dicarboxylic anhydride structures [—C (═O) —O—C (═O) —], dicarboximide structures [—C (═O) —N— C (= O)-] and the like. Examples of the substituent introduced into the heterocyclic ring when the heterocyclic ring has a substituent include a phenyl group, a naphthyl group, and an anthracenyl group.
　本発明で使用するアクリル樹脂は、特に限定されないが、アクリル基を有するカルボン酸、アクリル基を有するカルボン酸無水物、又はエポキシ基含有アクリレート化合物から選ばれる少なくとも１つを必須成分とする単独重合体又は共重合体が好ましい。 The acrylic resin used in the present invention is not particularly limited, but a homopolymer having at least one selected from a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound as an essential component. Or a copolymer is preferable.
　アクリル基を有するカルボン酸の具体例としては、（メタ）アクリル酸、マイレン酸、フマル酸、シトラコン酸、メサコン酸、グルタコン酸等；が挙げられ、
　アクリル基を有するカルボン酸無水物の具体例としては、無水マレイン酸、シトラコン酸無水物等；が挙げられ、
　エポキシ基含有アクリレート化合物の具体例としては、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル等；が挙げられる。
　これらのうち、（メタ）アクリル酸、無水マレイン酸、メタクリル酸グリシジル、メタクリル酸－６，７－エポキシヘプチル等が好ましい。本発明で「（メタ）アクリル」とは、メタクリルとアクリルのいずれかを意味する。 Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, and the like.
Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride, citraconic anhydride, and the like.
Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylate 3,4 -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. It is done.
Of these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable. In the present invention, “(meth) acryl” means either methacryl or acryl.
　アクリル樹脂は、不飽和カルボン酸、不飽和カルボン酸無水物及びエポキシ基含有不飽和化合物から選ばれる少なくとも一つと、その他のアクリレート系単量体又はアクリレート以外の共重合可能な単量体との共重合体であってもよい。その他のアクリレート系単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート； The acrylic resin is a copolymer of at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an epoxy group-containing unsaturated compound and another acrylate monomer or a copolymerizable monomer other than an acrylate. It may be a polymer. Other acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, alkyl (meth) acrylates such as isostearyl (meth) acrylate;
ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；フェノキシエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等のフェノキシアルキル（メタ）アクリレート；２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－プロポキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－メトキシブチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；ポリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレート等のポリアルキレングリコール（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、４－ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート等のシクロアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート等；を挙げることができる。これらのうち、ブチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレート及び２－エトキシエチル（メタ）アクリレート等が好ましい。 Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate Relate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, Polyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, Cycloalkyl (meth) acrylates such as cyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; benzyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Of these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.
　アクリレート以外の共重合可能な単量体としては、上記アクリル基を有するカルボン酸、アクリル基を有するカルボン酸無水物又はエポキシ基含有アクリレート化合物と共重合可能な化合物ならば特に制限はないが、例えば、ビニルベンジルメチルエーテル、ビニルグリシジルエーテル、スチレン、α－メチルスチレン、ブタジエン、イソプレン等のビニル基含有ラジカル重合性化合物が挙げられる。
　これらの化合物は、それぞれ単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　上記単量体の重合方法は、常法に従えばよく、例えば、懸濁重合法，乳化重合法，溶液重合法等が採用される。 The copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. And vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene.
These compounds may be used alone or in combination of two or more.
The monomer polymerization method may be in accordance with a conventional method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like is employed.
　カルド樹脂とは、カルド構造、即ち、環状構造を構成している４級炭素原子に二つの環状構造が結合した骨格構造、を有する樹脂である。カルド構造の一般的なものはフルオレン環にベンゼン環が結合したものである。
　環状構造を構成している４級炭素原子に二つの環状構造が結合した骨格構造の具体例としては、フルオレン骨格、ビスフェノールフルオレン骨格、ビスアミノフェニルフルオレン骨格、エポキシ基を有するフルオレン骨格、アクリル基を有するフルオレン骨格等が挙げられる。
　本発明で使用するカルド樹脂は、このカルド構造を有する骨格がそれに結合している官能基間の反応等により重合して形成される。カルド樹脂は、主鎖と嵩高い側鎖が一つの元素で繋がれた構造（カルド構造）をもち、主鎖に対してほぼ垂直方向に環状構造を有している。
　エポキシグリシジルエーテル構造を有するカルド構造の例を式（ＩＩＩ）に示す。 A cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. A common cardo structure is a fluorene ring bonded to a benzene ring.
Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
The cardo resin used in the present invention is formed by polymerizing the skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.
An example of a cardo structure having an epoxy glycidyl ether structure is shown in Formula (III).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式（ＩＩＩ）中、ｎは０～１０の整数を表す。） (In formula (III), n represents an integer of 0 to 10)
　カルド構造を有する単量体は、例えば、ビス（グリシジルオキシフェニル）フルオレン型エポキシ樹脂；ビスフェノールフルオレン型エポキシ樹脂とアクリル酸との縮合物；９，９－ビス（４－ヒドロキシフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン等のカルド構造含有ビスフェノ－ル類；９，９－ビス（シアノメチル）フルオレン等の９，９－ビス（シアノアルキル）フルオレン類；９，９－ビス（３－アミノプロピル）フルオレン等の９，９－ビス（アミノアルキル）フルオレン類；等が挙げられる。
　カルド樹脂は、カルド構造を有する単量体を重合して得られる重合体であるが、その他の共重合可能な単量体との共重合体であってもよい。
　上記単量体の重合方法は、常法に従えばよく、例えば、開環重合法や付加重合法等が採用される。 Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenolfluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
The cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.
　本発明で使用するポリシロキサンの構造は特に限定されないが、好ましくは式（ＩＶ）で表されるオルガノシランの１種または２種以上を混合、反応させることによって得られるポリシロキサンが挙げられる。 The structure of the polysiloxane used in the present invention is not particularly limited, but a polysiloxane obtained by mixing and reacting one or more of organosilanes represented by the formula (IV) is preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式（ＩＶ）中、Ｒ９は水素、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数６～１５のアリール基のいずれかを表し、複数のＲ９はそれぞれ同じであっても異なっていても良い。Ｒ１０は水素、炭素数１～６のアルキル基、炭素数１～６のアシル基、炭素数６～１５のアリール基のいずれかを表し、複数のＲ１０はそれぞれ同じでも異なっていても良い。ｎは０から３の整数を表す。） (In the formula (IV), R 9 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, more R 9 each R 10 represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. R 10 may be the same or different, and n represents an integer of 0 to 3.)
　式（ＩＶ）のＲ９は水素、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数６～１５のアリール基のいずれかを表し、複数のＲ９はそれぞれ同じであっても異なっていても良い。また、これらのアルキル基、アルケニル基、アリール基はいずれも置換基を有していてもよく、また置換基を有していない無置換体であってもよく、組成物の特性に応じて選択できる。アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、ｎ－デシル基、トリフルオロメチル基、２，２，２－トリフルオロエチル基、３，３，３－トリフルオロプロピル基、３－グリシドキシプロピル基、２－（３，４－エポキシシクロヘキシル）エチル基、３－アミノプロピル基、３－メルカプトプロピル基、３－イソシアネートプロピル基が挙げられる。アルケニル基の具体例としては、ビニル基、３－アクリロキシプロピル基、３－メタクリロキシプロピル基が挙げられる。アリール基の具体例としては、フェニル基、トリル基、ｐ－ヒドロキシフェニル基、１－（ｐ－ヒドロキシフェニル）エチル基、２－（ｐ－ヒドロキシフェニル）エチル基、４－ヒドロキシ－５－（ｐ－ヒドロキシフェニルカルボニルオキシ）ペンチル基、ナフチル基が挙げられる。 R 9 in the formula (IV) represents a hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, more R 9 is the same respectively It can be different. In addition, these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be unsubstituted without a substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl, tolyl, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl, 2- (p-hydroxyphenyl) ethyl, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.
　式（ＩＶ）のＲ１０は水素、炭素数１～６のアルキル基、炭素数１～６のアシル基、炭素数６～１５のアリール基のいずれかを表し、複数のＲ１０はそれぞれ同じでも異なっていても良い。また、これらのアルキル基、アシル基はいずれも置換基を有していてもよく、また置換基を有していない無置換体であってもよく、組成物の特性に応じて選択できる。アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基が挙げられる。アシル基の具体例としては、アセチル基が挙げられる。アリール基の具体例としてはフェニル基が挙げられる。
　式（ＩＶ）のｎは０から３の整数を表す。ｎ＝０の場合は４官能性シラン、ｎ＝１の場合は３官能性シラン、ｎ＝２の場合は２官能性シラン、ｎ＝３の場合は１官能性シランである。 R 10 is hydrogen Formula (IV), an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, even more R 10 is the same as each It may be different. In addition, these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.
N in the formula (IV) represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.
　式（ＩＶ）で表されるオルガノシランの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラアセトキシシラン、テトラフェノキシシランなどの４官能性シラン；メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリｎ－ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、エチルトリｎ－ブトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、ｎ－ブチルトリメトキシシラン、ｎ－ブチルトリエトキシシラン、ｎ－へキシルトリメトキシシラン、ｎ－へキシルトリエトキシシラン、デシルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ｐ－ヒドロキシフェニルトリメトキシシラン、１－（ｐ－ヒドロキシフェニル）エチルトリメトキシシラン、２－（ｐ－ヒドロキシフェニル）エチルトリメトキシシラン、４－ヒドロキシ－５－（ｐ－ヒドロキシフェニルカルボニルオキシ）ペンチルトリメトキシシラン、トリフルオロメチルトリメトキシシラン、トリフルオロメチルトリエトキシシラン、３，３，３－トリフルオロプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－メルカプトプロピルトリメトキシシランなどの３官能性シラン；ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジアセトキシシラン、ジｎ－ブチルジメトキシシラン、ジフェニルジメトキシシランなどの２官能性シラン；トリメチルメトキシシラン、トリｎ－ブチルエトキシシランなどの１官能性シラン；が挙げられる。 Specific examples of the organosilane represented by the formula (IV) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltrisilane Isopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Trifunctional silanes such as silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxy And bifunctional silanes such as silane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.
　これらのオルガノシランのうち、本発明の樹脂組成物から得られる樹脂膜の耐クラック性や硬度の点から３官能性シランが好ましく用いられる。また、これらのオルガノシランは単独で使用しても、２種以上を組み合わせて使用しても良い。 Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. These organosilanes may be used alone or in combination of two or more.
　本発明におけるポリシロキサンは、上述のオルガノシランを加水分解および部分縮合させることにより得られる。加水分解および部分縮合には一般的な方法を用いることができる。例えば、混合物に溶媒、水、必要に応じて触媒を添加し、加熱攪拌する。攪拌中、必要に応じて蒸留によって加水分解副生物（メタノールなどのアルコール）や縮合副生物（水）を留去してもよい。 The polysiloxane in the present invention can be obtained by hydrolyzing and partially condensing the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.
　本発明で使用するポリイミドは、テトラカルボン酸無水物とジアミンを反応させて得たポリイミド前駆体を熱処理することで得ることができる。ポリイミド樹脂を得るための前駆体としては、ポリアミド酸、ポリアミド酸エステル、ポリイソイミド、ポリアミド酸スルホンアミド等がある。
　ポリイミドの原料として使用できる酸二無水物としては、具体的には、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’－ベンゾフェノンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、ビス（３，４－ジカルボキシフェニル）メタン二無水物、ビス（２，３－ジカルボキシフェニル）メタン二無水物、ビス（３，４－ジカルボキシフェニル）スルホン二無水物、ビス（３，４－ジカルボキシフェニル）エーテル二無水物、１，２，５，６－ナフタレンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、２，３，５，６－ピリジンテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物等の芳香族テトラカルボン酸二無水物や、ブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物等の脂肪族のテトラカルボン酸二無水物等を挙げることができる。これらの酸二無水物は、単独又は２種以上を組み合わせて使用できる。 The polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Examples of the precursor for obtaining the polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
Specific examples of acid dianhydrides that can be used as raw materials for polyimide include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) ) Methane dianhydride, bis (2 , 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Aromatic tetracarboxylic dianhydrides such as carboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2, Examples thereof include aliphatic tetracarboxylic dianhydrides such as 3,4-cyclopentanetetracarboxylic dianhydride. These acid dianhydrides can be used alone or in combination of two or more.
　ポリイミドの原料として使用できるジアミンの具体的な例としては、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、３，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルホン、３，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルフィド、１，４－ビス（４－アミノフェノキシ）ベンゼン、ベンジン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、１，５－ナフタレンジアミン、２，６－ナフタレンジアミン、ビス（４－アミノフェノキシフェニル）スルホン、ビス（３－アミノフェノキシフェニル）スルホン、ビス（４－アミノフェノキシ）ビフェニル、ビス｛４－（４－アミノフェノキシ）フェニル｝エーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジエチル－４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジエチル－４，４’－ジアミノビフェニル、２，２’，３，３’－テトラメチル－４，４’－ジアミノビフェニル、３，３’，４，４’－テトラメチル－４，４’－ジアミノビフェニル、２，２’－ジ（トリフルオロメチル）－４，４’－ジアミノビフェニル；あるいはこれらの化合物の芳香族環にアルキル基やハロゲン原子で置換した化合物；や、脂肪族のシクロヘキシルジアミン、メチレンビスシクロヘキシルアミン；等が挙げられる。これらのジアミンは、単独又は２種以上を組み合わせて使用できる。 Specific examples of diamines that can be used as a raw material for polyimide include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl ,Screw{ -(4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4 ' -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4 '-Diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl; or these compounds A compound in which the aromatic ring is substituted with an alkyl group or a halogen atom; aliphatic cyclohexyldiamine, methylenebiscyclohexylamine; and the like. These diamines can be used alone or in combination of two or more.
　本発明で使用するポリイミドは公知の方法によって合成される。すなわち、テトラカルボン酸二無水物とジアミンとを選択的に組み合わせ、これらをＮ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホロトリアミド、γ－ブチロラクトン、シクロペンタノン等の極性溶媒中で反応させる等、公知の方法によって合成される。 The polyimide used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as γ-butyrolactone and cyclopentanone.
　本発明で使用されるバインダー樹脂（Ａ）の重量平均分子量（Ｍｗ）は、通常、１，０００～１，０００，０００、好ましくは１，５００～１００，０００、より好ましくは２，０００～１０，０００の範囲である。
　バインダー樹脂（Ａ）の分子量分布は、重量平均分子量／数平均分子量（Ｍｗ／Ｍｎ）比で、通常、４以下、好ましくは３以下、より好ましくは２．５以下である。
　バインダー樹脂（Ａ）の重量平均分子量（Ｍｗ）や分子量分布は、ゲルパーミエーションクロマトグラフィーを用いて、測定することができる。例えば、テトラヒドロフラン等の溶媒を溶離液とし、ポリスチレン換算分子量として求めることができる。 The weight average molecular weight (Mw) of the binder resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10 , 000.
The molecular weight distribution of the binder resin (A) is a weight average molecular weight / number average molecular weight (Mw / Mn) ratio, and is usually 4 or less, preferably 3 or less, more preferably 2.5 or less.
The weight average molecular weight (Mw) and molecular weight distribution of the binder resin (A) can be measured using gel permeation chromatography. For example, it can be determined as a molecular weight in terms of polystyrene using a solvent such as tetrahydrofuran as an eluent.
　酸性基を有する化合物（Ｂ）
　本発明において、樹脂組成物の必須成分として、酸性基を有する化合物（Ｂ）を使用する。
　酸性基を有する化合物（Ｂ）は、酸性基を有するものであればよく、特に限定されないが、好ましくは脂肪族化合物、芳香族化合物、複素環化合物であり、更に好ましくは芳香族化合物、複素環化合物である。酸性基を有する化合物（Ｂ）として前記化合物を用いることにより、密着性をさらに向上させることができる。
　これらの化合物（Ｂ）は、それぞれ単独で又は２種以上を組み合わせて用いることができる Compound (B) having acidic group
In the present invention, the compound (B) having an acidic group is used as an essential component of the resin composition.
The compound (B) having an acidic group is not particularly limited as long as it has an acidic group, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound, and more preferably an aromatic compound or a heterocyclic ring. A compound. By using the compound as the compound (B) having an acidic group, adhesion can be further improved.
These compounds (B) can be used alone or in combination of two or more.
　酸性基の数は、特に限定されないが、２つ以上の酸性基を有するものが好ましく、特に２つの酸性基を有するものが好ましい。酸性基は、互いに同一であっても異なっていてもよい。
　酸性基は、酸性の官能基であればよく、その具体例としては、スルホン酸基、リン酸基等の強酸性基；カルボキシ基、チオール基及びカルボキシメチレンチオ基等の弱酸性基；が挙げられる。これらの中でも、密着性をさらに向上できる点で、カルボキシ基、チオール基またはカルボキシメチレンチオ基が好ましく、カルボキシ基が特に好ましい。また、これらの酸性基の中でも、現像感度や保存安定性の観点より、酸解離定数ｐＫａが３．５以上５．０以下の範囲にあるものが好ましい。なお、酸性基が２つ以上ある場合は第一解離定数ｐＫａ１を酸解離定数とする。なお、ｐＫａは、希薄水溶液条件下で、酸解離定数Ｋａ＝［Ｈ３Ｏ＋］［Ｂ－］／［ＢＨ］である。ここでＢＨは有機酸を表し、Ｂ－は有機酸の共役塩基を表す。ｐＫａはｐＫａ＝－ｌｏｇＫａである。
　また、ｐＫａの測定方法は、例えばｐＨメーターを用いて水素イオン濃度を測定し、該当物質の濃度と水素イオン濃度から算出することができる。
　本発明において、これらの酸性基を使用することにより、本発明の樹脂組成物から形成される樹脂膜は、密着性に優れる。 The number of acidic groups is not particularly limited, but those having two or more acidic groups are preferable, and those having two acidic groups are particularly preferable. The acidic groups may be the same as or different from each other.
The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group. It is done. Among these, a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable in that the adhesion can be further improved. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 or more and 5.0 or less are preferable from the viewpoint of development sensitivity and storage stability. When there are two or more acidic groups, the first dissociation constant pKa1 is defined as the acid dissociation constant. Note that pKa is an acid dissociation constant Ka = [H 3 O + ] [B − ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B − represents a conjugate base of the organic acid. pKa is pKa = −logKa.
Moreover, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a applicable substance, and hydrogen ion concentration.
In this invention, the resin film formed from the resin composition of this invention is excellent in adhesiveness by using these acidic groups.
　本発明において、前記化合物（Ｂ）は、酸性基以外の置換基を有していてもよい。
　このような置換基としては、アルキル基、アリール基等の炭化水素基；のほか、ハロゲン原子；アルコキシ基、アリールオキシ基、アシルオキシ基、ヘテロ環オキシ基；アルキル基、アリール基又は複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基；アルキルチオ基、アリールチオ基、ヘテロ環チオ基；等のプロトンを有しない極性基、これらのプロトンを有しない極性基で置換された炭化水素基、等を挙げることができる。 In the present invention, the compound (B) may have a substituent other than an acidic group.
Examples of such substituents include hydrocarbon groups such as alkyl groups and aryl groups; halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; alkyl groups, aryl groups, and heterocyclic groups. Substituted amino groups, acylamino groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups; alkylthio groups, arylthio groups, heterocyclic thio groups; polar groups having no protons, etc. And a hydrocarbon group substituted with a polar group having no proton.
　化合物（Ｂ）の具体例としては、メタン酸、エタン酸、プロパン酸、ブタン酸、ペンタン酸、ブタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、グリコール酸、グリセリン酸、エタン二酸（「シュウ酸」ともいう。）、プロパン二酸（「マロン酸」ともいう。）、ブタン二酸（「コハク酸」ともいう。）、ペンタン二酸、ヘキサン二酸（「アジピン酸」ともいう。）、１，２―シクロヘキサンジカルボン酸、２－オキソプロパン酸、２－ヒドロキシブタン二酸、２－ヒドロキシプロパントリカルボン酸、メルカプトコハク酸、ジメルカプトコハク酸、２，３－ジメルカプト－１－プロパノール、１，２，３－トリメルカプトプロパン、２，３，４－トリメルカプト－１－ブタノール、２，４－ジメルカプト－１，３－ブタンジオール、１，３，４－トリメルカプト－２－ブタノール、３，４－ジメルカプト－１，２－ブタンジオール、１，５－ジメルカプト－３－チアペンタン等の脂肪族化合物； Specific examples of the compound (B) include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glyceric acid, and ethane. Diacid (also called “oxalic acid”), propanedioic acid (also called “malonic acid”), butanedioic acid (also called “succinic acid”), pentanedioic acid, hexanedioic acid (“adipic acid”) Also, 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1- Propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3- Butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, aliphatic compounds such as 1,5-dimercapto-3-Chiapentan;
安息香酸、ｐ－ヒドロキシベンゼンカルボン酸、ｏ－ヒドロキシベンゼンカルボン酸、２－ナフタレンカルボン酸、メチル安息香酸、ジメチル安息香酸、トリメチル安息香酸、３－フェニルプロパン酸、２－ヒドロキシ安息香酸、ジヒドロキシ安息香酸、ジメトキシ安息香酸、ベンゼン－１，２－ジカルボン酸（「フタル酸」ともいう。）、ベンゼン－１，３－ジカルボン酸（「イソフタル酸」ともいう。）、ベンゼン－１，４－ジカルボン酸（「テレフタル酸」ともいう。）、ベンゼン－１，２，３－トリカルボン酸、ベンゼン－１，２，４－トリカルボン酸、ベンゼン－１，３，５－トリカルボン酸、ベンゼンヘキサカルボン酸、ビフェニル－２，２’－ジカルボン酸、２－（カルボキシメチル）安息香酸、３－（カルボキシメチル）安息香酸、４－（カルボキシメチル）安息香酸、２－（カルボキシカルボニル）安息香酸、３－（カルボキシカルボニル）安息香酸、４－（カルボキシカルボニル）安息香酸、２－メルカプト安息香酸、４－メルカプト安息香酸、２－メルカプト－６－ナフタレンカルボン酸、２－メルカプト－７－ナフタレンカルボン酸、１，２－ジメルカプトベンゼン、１，３－ジメルカプトベンゼン、１，４－ジメルカプトベンゼン、１，４－ナフタレンジチオール、１，５－ナフタレンジチオール、２，６－ナフタレンジチオール、２，７－ナフタレンジチオール、１，２，３－トリメルカプトベンゼン、１，２，４－トリメルカプトベンゼン、１，３，５－トリメルカプトベンゼン、１，２，３－トリス（メルカプトメチル）ベンゼン、１，２，４－トリス（メルカプトメチル）ベンゼン、１，３，５－トリス（メルカプトメチル）ベンゼン、１，２，３－トリス（メルカプトエチル）ベンゼン、１，２，４－トリス（メルカプトエチル）ベンゼン、１，３，５－トリス（メルカプトエチル）ベンゼン等の芳香族化合物； Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid ( Also referred to as “terephthalic acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2 , 2'-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) an Perfume acid, 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalene Dithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-tri Mercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4- Lis (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,3 Aromatic compounds such as 5-tris (mercaptoethyl) benzene;
ニコチン酸、イソニコチン酸、２－フロ酸、ピロール－２，３－ジカルボン酸、ピロール－２，４－ジカルボン酸、ピロール－２，５－ジカルボン酸、ピロール－３，４－ジカルボン酸、イミダゾール－２，４－ジカルボン酸、イミダゾール－２，５－ジカルボン酸、イミダゾール－４，５－ジカルボン酸、ピラゾール－３，４－ジカルボン酸、ピラゾール－３，５－ジカルボン酸等の窒素原子を含む五員複素環化合物；チオフェン－２，３－ジカルボン酸、チオフェン－２，４－ジカルボン酸、チオフェン－２，５－ジカルボン酸、チオフェン－３，４－ジカルボン酸、チアゾール－２，４－ジカルボン酸、チアゾール－２，５－ジカルボン酸、チアゾール－４，５－ジカルボン酸、イソチアゾール－３，４－ジカルボン酸、イソチアゾール－３，５－ジカルボン酸、１，２，４－チアジアゾール－２，５－ジカルボン酸、１，３，４－チアジアゾール－２，５－ジカルボン酸、３－アミノ－５－メルカプト－１，２，４－チアジアゾール、２－アミノ－５－メルカプト－１，３，４－チアジアゾール、３，５－ジメルカプト－１，２，４－チアジアゾール、２，５－ジメルカプト－１，３，４－チアジアゾール、３－（５－メルカプト－１，２，４－チアジアゾール－３－イルスルファニル）コハク酸、２－（５－メルカプト－１，３，４－チアジアゾール－２－イルスルファニル）コハク酸、（５－メルカプト－１，２，４－チアジアゾール－３－イルチオ）酢酸、（５－メルカプト－１，３，４－チアジアゾール－２－イルチオ）酢酸、３－（５－メルカプト－１，２，４－チアジアゾール－３－イルチオ）プロピオン酸、２－（５－メルカプト－１，３，４－チアジアゾール－２－イルチオ）プロピオン酸、３－（５－メルカプト－１，２，４－チアジアゾール－３－イルチオ）コハク酸、２－（５－メルカプト－１，３，４－チアジアゾール－２－イルチオ）コハク酸、４－（３－メルカプト－１，２，４－チアジアゾール－５－イル）チオブタンスルホン酸、４－（２－メルカプト－１，３，４－チアジアゾール－５－イル）チオブタンスルホン酸等の窒素原子と硫黄原子を含む五員複素環化合物； Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole 5-membered containing nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds: thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole -3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2, 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1 , 2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4 Thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4 -5-membered heterocyclic compounds containing nitrogen and sulfur atoms such as (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid;
ピリジン－２，３－ジカルボン酸、ピリジン－２，４－ジカルボン酸、ピリジン－２，５－ジカルボン酸、ピリジン－２，６－ジカルボン酸、ピリジン－３，４－ジカルボン酸、ピリジン－３，５－ジカルボン酸、ピリダジン－３，４－ジカルボン酸、ピリダジン－３，５－ジカルボン酸、ピリダジン－３，６－ジカルボン酸、ピリダジン－４，５－ジカルボン酸、ピリミジン－２，４－ジカルボン酸、ピリミジン－２，５－ジカルボン酸、ピリミジン－４，５－ジカルボン酸、ピリミジン－４，６－ジカルボン酸、ピラジン－２，３－ジカルボン酸、ピラジン－２，５－ジカルボン酸、ピリジン－２，６－ジカルボン酸、トリアジン－２，４－ジカルボン酸、２－ジエチルアミノ－４，６－ジメルカプト－ｓ－トリアジン、２－ジプロピルアミノ－４，６－ジメルカプト－ｓ－トリアジン、２－ジブチルアミノ－４，６－ジメルカプト－ｓ－トリアジン、２－アニリノ－４，６－ジメルカプト－ｓ－トリアジン、２，４，６－トリメルカプト－ｓ－トリアジン等の窒素原子を含む六員複素環化合物；が挙げられる。
　これらの中でも、樹脂組成物から形成される樹脂膜を、基板に対する密着性が良好なものとすることができるという観点から、酸性基の数は、２つ以上であることが好ましく、２つが特に好ましい。
　酸性基を２つ有する化合物としては、エタン二酸、プロパン二酸、ブタン二酸、ペンタン二酸、ヘキサン二酸、１，２―シクロヘキサンジカルボン酸、ベンゼン－１，２－ジカルボン酸（「フタル酸」ともいう。）、ベンゼン－１，３－ジカルボン酸（「イソフタル酸」ともいう。）、ベンゼン－１，４－ジカルボン酸（「テレフタル酸」ともいう。）ビフェニル－２，２’－ジカルボン酸、２－（カルボキシメチル）安息香酸、３－（カルボキシメチル）安息香酸、４－（カルボキシメチル）安息香酸、２－メルカプト安息香酸、４－メルカプト安息香酸、２－メルカプト－６－ナフタレンカルボン酸、２－メルカプト－７－ナフタレンカルボン酸、１，２－ジメルカプトベンゼン、１，３－ジメルカプトベンゼン、１，４－ジメルカプトベンゼン、１，４－ナフタレンジチオール、１，５－ナフタレンジチオール、２，６－ナフタレンジチオール、２，７－ナフタレンジチオールの２つの酸性基を有する芳香族化合物；ピロール－２，３－ジカルボン酸、ピロール－２，４－ジカルボン酸、ピロール－２，５－ジカルボン酸、ピロール－３，４－ジカルボン酸、イミダゾール－２，４－ジカルボン酸、イミダゾール－２，５－ジカルボン酸、イミダゾール－４，５－ジカルボン酸、ピラゾール－３，４－ジカルボン酸、ピラゾール－３，５－ジカルボン、チオフェン－２，３－ジカルボン酸、チオフェン－２，４－ジカルボン酸、チオフェン－２，５－ジカルボン酸、チオフェン－３，４－ジカルボン酸、チアゾール－２，４－ジカルボン酸、チアゾール－２，５－ジカルボン酸、チアゾール－４，５－ジカルボン酸、イソチアゾール－３，４－ジカルボン酸、イソチアゾール－３，５－ジカルボン酸、１，２，４－チアジアゾール－２，５－ジカルボン酸、１，３，４－チアジアゾール－２，５－ジカルボン酸、（５－メルカプト－１，２，４－チアジアゾール－３－イルチオ）酢酸、（５－メルカプト－１，３，４－チアジアゾール－２－イルチオ）酢酸、ピリジン－２，３－ジカルボン酸、ピリジン－２，４－ジカルボン酸、ピリジン－２，５－ジカルボン酸、ピリジン－２，６－ジカルボン酸、ピリジン－３，４－ジカルボン酸、ピリジン－３，５－ジカルボン酸、ピリダジン－３，４－ジカルボン酸、ピリダジン－３，５－ジカルボン酸、ピリダジン－３，６－ジカルボン酸、ピリダジン－４，５－ジカルボン酸、ピリミジン－２，４－ジカルボン酸、ピリミジン－２，５－ジカルボン酸、ピリミジン－４，５－ジカルボン酸、ピリミジン－４，６－ジカルボン酸、ピラジン－２，３－ジカルボン酸、ピラジン－２，５－ジカルボン酸、ピリジン－２，６－ジカルボン酸、トリアジン－２，４－ジカルボン酸の２つの酸性基を有する複素環化合物；が好ましい。
　これらの化合物を使用することにより、樹脂組成物から形成される樹脂膜と基板との密着性が高いという効果を得ることができる。 Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, from the viewpoint that the resin film formed from the resin composition can have good adhesion to the substrate, the number of acidic groups is preferably two or more, and particularly preferably two preferable.
The compounds having two acidic groups include ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (“phthalic acid”). ), Benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”), biphenyl-2,2′-dicarboxylic acid. 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobe , Aromatic compounds having two acidic groups, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol; pyrrole-2,3-dicarboxylic acid, pyrrole -2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5- Dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3 , 4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid Thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4- Thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, pyridine-2 , 3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid , Pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarbo Acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2 , 5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, and heterocyclic compounds having two acidic groups of triazine-2,4-dicarboxylic acid.
By using these compounds, the effect that the adhesiveness of the resin film and board | substrate formed from a resin composition is high can be acquired.
　本発明の樹脂組成物における、酸性基を有する化合物（Ｂ）の含有量は、バインダー樹脂（Ａ）１００重量部に対して、通常、５～４５重量部、好ましくは７～４０重量部、更に好ましくは１０～３０重量部の範囲である。酸性基を有する化合物（Ｂ）の使用量がこの範囲にあれば、液状安定性に優れる樹脂組成物を得ることができる。 The content of the compound (B) having an acidic group in the resin composition of the present invention is usually 5 to 45 parts by weight, preferably 7 to 40 parts by weight, more preferably 100 parts by weight of the binder resin (A). The range is preferably 10 to 30 parts by weight. If the usage-amount of the compound (B) which has an acidic group exists in this range, the resin composition which is excellent in liquid stability can be obtained.
　化合物（Ｄ）
　本発明において、樹脂組成物の必須成分として、ケイ素原子、チタン原子、アルミニウム原子、ジルコニウム原子から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を使用する。 Compound (D)
In the present invention, as an essential component of the resin composition, a compound (D) having one atom selected from a silicon atom, a titanium atom, an aluminum atom and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom Is used.
　これらの中でも、ケイ素原子又はチタン原子に結合したヒドロカルビルオキシ基を有する化合物が好ましい。
　また、前記ヒドロカルビルオキシ基は、炭素数１～１８のヒドロカルビルオキシ基であることが好ましい。 Among these, compounds having a hydrocarbyloxy group bonded to a silicon atom or a titanium atom are preferable.
The hydrocarbyloxy group is preferably a hydrocarbyloxy group having 1 to 18 carbon atoms.
　化合物（Ｄ）は、バインダー樹脂（Ａ）が、プロトン性極性基を有するものであるとき、プロトン性極性基と反応し得る官能基を有することが、特に好ましい。
　このプロトン性極性基と反応し得る官能基は、イソシアネート基、メルカプト基、エポキシ基、又はアミノ基であることが好ましく、エポキシ基であることが、更に好ましい。 When the binder resin (A) has a protic polar group, the compound (D) particularly preferably has a functional group capable of reacting with the protic polar group.
The functional group capable of reacting with the protic polar group is preferably an isocyanate group, a mercapto group, an epoxy group, or an amino group, and more preferably an epoxy group.
　化合物（Ｄ）の具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラ－ｎ－プロポキシシラン、テトラ－ｉ－プロポキシシラン、テトラ－ｎ－ブトキシシランなどのテトラアルコキシシラン類、
メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、ｉ－プロピルトリメトキシシラン、ｉ－プロピルトリエトキシシラン、ｎ－ブチルトリメトキシシラン、ｎ－ブチルトリエトキシシラン、ｎ－ペンチルトリメトキシシラン、ｎ－ヘキシルトリメトキシシラン、ｎ－ヘプチルトリメトキシシラン、ｎ－オクチルトリメトキシシラン、ｎ－デシルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、３－クロロプロピルトリメトキシシラン、３－クロロプロピルトリエトキシシラン、３，３，３－トリフルオロプロピルトリメトキシシラン、３，３，３－トリフルオロプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、２－ヒドロキシエチルトリメトキシシラン、２－ヒドロキシエチルトリエトキシシラン、２－ヒドロキシプロピルトリメトキシシラン、２－ヒドロキシプロピルトリエトキシシラン、３－ヒドロキシプロピルトリメトキシシラン、３－ヒドロキシプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－イソシアナートプロピルトリメトキシシラン、３－イソシアナートプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、３－（メタ）アクリルオキシプロピルトリメトキシシラン、３－（メタ）アクリルオキシプロピルトリエトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－エチル（トリメトキシシリルプロポキシメチル）オキセタン、３－エチル（トリエトキシシリルプロポキシメチル）オキセタン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、ビス（トリエトキシシリルプロピル）テトラスルフィドなどのトリアルコキシシラン類、
ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ－ｎ－プロピルジメトキシシラン、ジ－ｎ－プロピルジエトキシシラン、ジ－ｉ－プロピルジメトキシシラン、ジ－ｉ－プロピルジエトキシシラン、ジ－ｎ－ブチルジメトキシシラン、ジ－ｎ－ペンチルジメトキシシラン、ジ－ｎ－ペンチルジエトキシシラン、ジ－ｎ－ヘキシルジメトキシシラン、ジ－ｎ－ヘキシルジエトキシシラン、ジ－ｎ－へプチルジメトキシシラン、ジ－ｎ－ヘプチルジエトキシシラン、ジ－ｎ－オクチルジメトキシシラン、ジ－ｎ－オクチルジエトキシシラン、ジ－ｎ－シクロヘキシルジメトキシシラン、ジ－ｎ－シクロヘキシルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－メタクリルオキシプロピルメチルジメトキシシラン、３－アクリルオキシプロピルメチルジメトキシシラン、３－メタクリルオキシプロピルメチルジエトキシシラン、３－アクリルオキシプロピルメチルジエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシランなどのジアルコキシシラン類、
の他、メチルトリアセチルオキシシラン、ジメチルジアセチルオキシシラン、商品名Ｘ－１２－４１４、ＫＢＰ－４４（信越化学工業株式会社製）、２１７ＦＬＡＫＥ、２２０ＦＬＡＫＥ、２３３ＦＬＡＫＥ、ｚ６０１８（東レダウコーニング株式会社製）等のケイ素原子含有化合物； Specific examples of the compound (D) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, fluorine Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropi Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Trialkoxysilanes such as oxetane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane Dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
In addition, methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (manufactured by Toray Dow Corning Co., Ltd.), etc. A silicon atom-containing compound of
テトラ－ｉ－プロポキシチタン、テトラ－ｎ－ブトキシチタン、テトラキス（２－エチルヘキシルオキシ）チタン、チタニウム－ｉ－プロポキシオクチレングリコレート、ジ－ｉ－プロポキシ・ビス（アセチルアセトナト）チタン、プロパンジオキシチタンビス（エチルアセトアセテート）、トリ－ｎ－ブトキシチタンモノステアレート、ジ－ｉ－プロポキシチタンジステアレート、チタニウムステアレート、ジ－ｉ－プロポキシチタンジイソステアレート、（２－ｎ－ブトキシカルボニルベンゾイルオキシ）トリブトキシチタン、ジ－ｎ－ブトキシ・ビス（トリエタノールアミナト）チタンの他、プレンアクトシリーズ（味の素ファインテクノ株式会社製）等のチタン原子含有化合物；
アセトアルコキシアルミウムジイソプロピレート等のアルミニウム原子含有化合物；
テトラ－ｎ－プロポキシジルコニウム、テトラ－ｎ－ブトキシジルコニウム、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス（エチルアセトアセテート）、ジルコニウムジブトキシビス（エチルアセトアセテート）、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシステアレート等のジルコニウム原子含有化合物；
が挙げられる。 Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedioxy Titanium bis (ethyl acetoacetate), tri-n-butoxy titanium monostearate, di-i-propoxy titanium distearate, titanium stearate, di-i-propoxy titanium diisostearate, (2-n-butoxycarbonylbenzoyl) In addition to oxy) tributoxytitanium, di-n-butoxybis (triethanolaminato) titanium, and the preneact series (manufactured by Ajinomoto Fine Techno Co., Ltd.)
Aluminum atom-containing compounds such as acetoalkoxyaluminum diisopropylate;
Tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), Zirconium atom-containing compounds such as zirconium tetraacetylacetonate and zirconium tributoxy systemate;
Is mentioned.
　これらの中でも、ケイ素原子含有化合物、チタン原子含有化合物が好ましく、ケイ素原子含有化合物がより好ましく、プロトン性極性基と反応し得る官能基を有するケイ素原子含有化合物が特に好ましい。前記官能基を有することにより、本発明の樹脂組成物を、基板に積層した際の密着性をより向上させることができる。
　前記プロトン性極性基と反応し得る官能基としては、アミノ基、メルカプト基、イソシアナート基、グリシドキシ基、エポキシ基、ウレイド基が挙げられ、グリシドキシ基やエポキシ基が好ましい。
　前記プロトン性極性基と反応し得る官能基を有する化合物の具体例としては、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－イソシアナートプロピルトリメトキシシラン、３－イソシアナートプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－トリエトキシシリル－ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシランが特に好ましい。
　これらの化合物（Ｄ）は、それぞれ単独で又は２種以上を組み合わせて用いることができる。 Among these, a silicon atom-containing compound and a titanium atom-containing compound are preferable, a silicon atom-containing compound is more preferable, and a silicon atom-containing compound having a functional group capable of reacting with a protic polar group is particularly preferable. By having the said functional group, the adhesiveness at the time of laminating | stacking the resin composition of this invention on a board | substrate can be improved more.
Examples of the functional group capable of reacting with the protic polar group include an amino group, a mercapto group, an isocyanate group, a glycidoxy group, an epoxy group, and a ureido group, and a glycidoxy group and an epoxy group are preferable.
Specific examples of the compound having a functional group capable of reacting with the protic polar group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, n-2- (aminoethyl) -3-aminopropyltri Methoxysilane, n-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3 -Ureido Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-triethoxysilyl-n- (1,3-dimethyl-butylidene) propylamine, n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane Is particularly preferred.
These compounds (D) can be used alone or in combination of two or more.
　本発明の樹脂組成物における化合物（Ｄ）の含有量は、バインダー樹脂（Ａ）１００重量部に対して、１～４０重量部、好ましくは３～３０重量部、より好ましくは５～２５重量部の範囲である。化合物（Ｄ）の使用量がこの範囲にあれば、樹脂組成物から形成される樹脂膜と基板との密着性が十分に高くなるため、好ましい。 The content of the compound (D) in the resin composition of the present invention is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the binder resin (A). Range. If the usage-amount of a compound (D) exists in this range, since the adhesiveness of the resin film formed from a resin composition and a board | substrate becomes high enough, it is preferable.
　本発明において、前記化合物（Ｂ）と化合物（Ｄ）の合計含有量は、バインダー樹脂（Ａ）１００重量部に対して、１０～５０重量部、好ましくは１３～４０重量部、特に好ましくは１５～３５重量部である。前記合計量が１０重量部未満であると、密着性向上の効果が得られず、逆に５０重量部を超えると感放射線化合物（Ｅ）を添加して樹脂組成物に感光性を付与した際に、塗膜の現像時の減膜量が大きくなる。
　また、本発明において、前記化合物（Ｂ）の含有量は、化合物（Ｄ）の含有量以上であることが好ましく、前記化合物（Ｂ）の含有量は、化合物（Ｄ）の含有量より多いことがより好ましい。化合物（Ｂ）の含有量が、化合物（Ｄ）の含有量以上であることにより、密着性向上に高い効果を示す。 In the present invention, the total content of the compound (B) and the compound (D) is 10 to 50 parts by weight, preferably 13 to 40 parts by weight, particularly preferably 15 parts per 100 parts by weight of the binder resin (A). ~ 35 parts by weight. When the total amount is less than 10 parts by weight, the effect of improving adhesion cannot be obtained. Conversely, when it exceeds 50 parts by weight, the radiation-sensitive compound (E) is added to impart photosensitivity to the resin composition. In addition, the amount of film reduction during development of the coating film increases.
Moreover, in this invention, it is preferable that content of the said compound (B) is more than content of a compound (D), and content of the said compound (B) is larger than content of a compound (D). Is more preferable. When content of a compound (B) is more than content of a compound (D), it shows a high effect on adhesive improvement.
　有機溶媒（Ｃ）
　本発明で使用される有機溶媒（Ｃ）は、特に限定されない。その具体例としては、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等のアルキレングリコール類；エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノｔ－ブチルエーテル、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、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等のアルキレングリコールモノエーテル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールエチルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールエチルメチルエーテル、トリプロピレングリコールエチルメチルエーテル等のアルキ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、ジ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ｎ－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ｉ－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ｎ－ブチルエーテルアセテート、プロピレングリコールモノｉ－ブチルエーテルアセテート、プロピレングリコールモノｓｅｃ－ブチルエーテルアセテート、プロピレングリコールモノｔ－ブチルエーテルアセテート等のアルキレングリコールモノアルキルエーテルエステル類；メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、４－ヒドロキシ－４－メチル－２－ペンタノン、シクロヘキサノン、シクロペンタノン等のケトン類；メタノール、エタノール、プロパノール、ブタノール、３－メトキシ－３－メチルブタノール等のアルコール類；テトラヒドロフラン、ジオキサン等の環状エーテル類；メチルセロソルブアセテート、エチルセロソルブアセテート等のセロソルブエステル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；酢酸エチル、酢酸ブチル、乳酸エチル、２－ヒドロキシ－２－メチルプロピオン酸メチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、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エチル、３－エトキシプロピオン酸メチル、γ－ブチロラクトン等のエステル類；Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド類；ジメチルスルホキシド等のスルホキシド類；等が挙げられる。
　この中でも、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロペンタノン、Ｎ－メチル－２－ピロリドンが好ましい。 Organic solvent (C)
The organic solvent (C) used in the present invention is not particularly limited. Specific examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono t-butyl ether, propylene glycol monoethyl Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Alkylene glycol monoethers such as diethyl glycol ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene Alkylene glycol dialkyl ethers such as glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether; propylene glycol monomethyl ether acetate, dipropylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono i-butyl ether acetate, propylene glycol mono alkylene glycol monoalkyl ether esters such as sec-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and cyclopentanone Class: methanol, ethanol, propanol, pig Alcohols such as diol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; aromatic hydrocarbons such as benzene, toluene and xylene; Ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 -Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone; N-methylformamide, N, N-dimethylformamide N- methyl-2-pyrrolidone, N- methylacetamide, N, N- amides dimethylacetamide; sulfoxides such as dimethyl sulfoxide; and the like.
Among these, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, and N-methyl-2-pyrrolidone are preferable.
　これらの有機溶媒は、それぞれ単独で用いてもよく又は２種以上を併用してもよい。有機溶媒（Ｃ）の使用量は、バインダー樹脂（Ａ）１００重量部に対して、通常、２０～１０，０００重量部、好ましくは５０～５，０００重量部、より好ましくは１００～１，０００重量部の範囲である。 These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent (C) used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts per 100 parts by weight of the binder resin (A). The range is parts by weight.
　感放射線化合物（Ｅ）
　本発明の樹脂組成物においては、感放射線化合物（Ｅ）をさらに含有してなることが好ましい。
　本発明で使用する感放射線化合物（Ｅ）は、紫外線や電子線等の放射線の照射により、化学反応を引き起こすことのできる化合物である。本発明において感放射線化合物（Ｅ）は、樹脂組成物から形成される樹脂膜のアルカリ溶解性を制御できるものが好ましい。
　本発明においては感放射線化合物（Ｅ）として光酸発生剤を使用することが好ましい。 Radiation sensitive compound (E)
The resin composition of the present invention preferably further comprises a radiation sensitive compound (E).
The radiation sensitive compound (E) used in the present invention is a compound capable of causing a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams. In the present invention, the radiation sensitive compound (E) is preferably one capable of controlling the alkali solubility of the resin film formed from the resin composition.
In the present invention, it is preferable to use a photoacid generator as the radiation-sensitive compound (E).
　感放射線化合物（Ｅ）としては、例えば、アセトフェノン化合物、トリアリールスルホニウム塩、キノンジアジド化合物等のアジド化合物等が挙げられるが、好ましくはアジド化合物、特に好ましくはキノンジアジド化合物である。 Examples of the radiation sensitive compound (E) include azide compounds such as acetophenone compounds, triarylsulfonium salts, quinonediazide compounds, and the like, preferably azide compounds, and particularly preferably quinonediazide compounds.
　キノンジアジド化合物としては、例えば、キノンジアジドスルホン酸ハライドとフェノール性水酸基を有する化合物とのエステル化合物を用いることができる。キノンジアジドスルホン酸ハライドの具体例としては、１，２－ナフトキノンジアジド－５－スルホン酸クロライド、１，２－ナフトキノンジアジド－４－スルホン酸クロライド、１，２－ベンゾキノンジアジド－５－スルホン酸クロライド等が挙げられる。フェノール性水酸基を有する化合物の代表例としては、１，１，３－トリス（２，５－ジメチル－４－ヒドロキシフェニル）－３－フェニルプロパン、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］ビスフェノール等が挙げられる。これら以外のフェノール性水酸基を有する化合物としては、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－ビス（４－ヒドロキシフェニル）プロパン、トリス（４－ヒドロキシフェニル）メタン、１，１，１－トリス（４－ヒドロキシ－３－メチルフェニル）エタン、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、ノボラック樹脂のオリゴマー、フェノール性水酸基を１つ以上有する化合物とジシクロペンタジエンとを共重合して得られるオリゴマー等が挙げられる。
　これらの中でも、１，２－ナフトキノンジアジド－５－スルホン酸クロライドとフェノール性水酸基を有する化合物との縮合物が好ましく、１，１，３－トリス（２，５－ジメチル－４－ヒドロキシフェニル）－３－フェニルプロパン（１モル）と１，２－ナフトキノンジアジド－５－スルホン酸クロライド（２．５モル）との縮合物がより好ましい。 As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1 -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) is more preferred.
　光酸発生剤としては、キノンジアジド化合物の他、オニウム塩、ハロゲン化有機化合物、α，α’－ビス（スルホニル）ジアゾメタン系化合物、α－カルボニル－α’－スルホニルジアゾメタン系化合物、スルホン化合物、有機酸エステル化合物、有機酸アミド化合物、有機酸イミド化合物等、公知のものを用いることができる。
　これらの感放射線化合物は、それぞれ単独で又は２種以上を組み合わせて用いることができる。 Photoacid generators include quinonediazide compounds, onium salts, halogenated organic compounds, α, α'-bis (sulfonyl) diazomethane compounds, α-carbonyl-α'-sulfonyldiazomethane compounds, sulfone compounds, organic acids Known compounds such as ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These radiation-sensitive compounds can be used alone or in combination of two or more.
　本発明の樹脂組成物における感放射線化合物（Ｅ）の含有量は、バインダー樹脂（Ａ）１００重量部に対して、１～１００重量部、好ましくは５～５０重量部、より好ましくは１０～４０重量部の範囲である。感放射線化合物（Ｅ）の使用量がこの範囲にあれば、任意の基板上に、本発明の樹脂組成物からなる樹脂膜を形成し、形成した樹脂膜をパターン化する際に、樹脂膜のうち放射線照射部と放射線未照射部との間における、現像液への溶解度差が大きくなり、現像によるパターン化が容易で、かつ、放射線感度も高くなるので好適である。 The content of the radiation sensitive compound (E) in the resin composition of the present invention is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the binder resin (A). The range is parts by weight. When the amount of the radiation sensitive compound (E) is within this range, a resin film made of the resin composition of the present invention is formed on an arbitrary substrate, and when the formed resin film is patterned, the resin film Among them, the difference in solubility in the developer between the radiation irradiated portion and the non-radiation irradiated portion is increased, which is preferable because patterning by development is easy and radiation sensitivity is increased.
　架橋剤（Ｆ）
　本発明において、樹脂組成物の成分として、架橋剤（Ｆ）をさらに含有することが好ましい。
　架橋剤（Ｆ）としては、バインダー樹脂（Ａ）と反応し得る官能基を、分子内に２つ以上、好ましくは３つ以上有するものが用いられる。架橋剤（Ｆ）の有する官能基はバインダー樹脂中の官能基や不飽和結合等と反応し得るものであれば、特に限定されないが、プロトン性極性基と反応し得るものが好ましい。
　かかる官能基としては、例えば、アミノ基、水酸基、エポキシ基、イソシアネート基等が挙げられ、より好ましくはアミノ基、エポキシ基及びイソシアネート基であり、更に好ましくはエポキシ基である。 Cross-linking agent (F)
In this invention, it is preferable to further contain a crosslinking agent (F) as a component of a resin composition.
As the crosslinking agent (F), one having two or more, preferably three or more functional groups capable of reacting with the binder resin (A) in the molecule is used. The functional group possessed by the cross-linking agent (F) is not particularly limited as long as it can react with a functional group or an unsaturated bond in the binder resin, but a functional group capable of reacting with a protic polar group is preferable.
Examples of such a functional group include an amino group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and still more preferably an epoxy group.
　架橋剤（Ｆ）の具体例としては、ヘキサメチレンジアミン等の脂肪族ポリアミン類；４，４’－ジアミノジフェニルエーテル、ジアミノジフェニルスルフォン等の芳香族ポリアミン類；２，６－ビス（４’－アジドベンザル）シクロヘキサノン、４，４’－ジアジドジフェニルスルフォン等のアジド類；ナイロン、ポリヘキサメチレンジアミンテレフタルアミド、ポリヘキサメチレンイソフタルアミド等のポリアミド類；Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ''，Ｎ''－（ヘキサアルコキシメチル）メラミン等のメラミン類；Ｎ，Ｎ’，Ｎ''，Ｎ'''－（テトラアルコキシメチル）グリコールウリル等のグリコールウリル類；エチレングリコールジ（メタ）アクリレート等のアクリレート化合物；ヘキサメチレンジイソシアネート系ポリイソシアネート、イソホロンジイソシアネート系ポリイソシアネート、トリレンジイソシアネート系ポリイソシアネート、水添ジフェニルメタンジイソシアネート等のイソシアネート系化合物；１，４－ジ－（ヒドロキシメチル）シクロヘキサン、１，４－ジ－（ヒドロキシメチル）ノルボルナン；１，３，４－トリヒドロキシシクロヘキサン；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、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、ポリフェノール型エポキシ樹脂、環状脂肪族エポキシ樹脂、脂肪族グリシジルエーテル、エポキシアクリレート重合体等のエポキシ化合物；を挙げることができる。 Specific examples of the crosslinking agent (F) include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, N Melamines such as ″-(hexaalkoxymethyl) melamine; Glycolurils such as N, N ′, N ″, N ′ ″-(tetraalkoxymethyl) glycoluril; Ethylene glycol di (meth) acrylate and the like Acrylate compound; hexamethylene diisocyanate polyisocyanate, a Isocyanate compounds such as holon diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3 , 4-trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate heavy And epoxy compounds such as coalescence;
　イソシアネート系化合物の具体例としては、住友バイエルウレタン社製のデスモジュールシリーズ（デスモジュールＢＬ３３７０、デスモジュールＶＰＬＳ２２５３）やクレランシリーズ（クレランＶ１、クレランＶＰＬＳ２２５６）、三井武田ケミカル社製のタケネートシリーズ（Ｂ－８１５Ｎ、Ｂ－８８２Ｎ、Ｂ－８７４Ｎ）、日本ポリウレタン社製のコロネートシリーズ（コロネートＬ）等が挙げられる。 Specific examples of the isocyanate compounds include the Death Module series (Desmodule BL3370, Deathmodule VPLS2253) and Clelan series (Clelan V1, Clelan VPLS2256) manufactured by Sumitomo Bayer Urethane Co., Ltd., and the Takenate series (B -815N, B-882N, B-874N), and Coronate series (Coronate L) manufactured by Nippon Polyurethane.
　メラミン類の具体例としては、「サイメル３００」、「サイメル３０１」、「サイメル３０３」、「サイメル３５０」、「サイメル１１２３」、「サイメル３７０」、「サイメル７７１」、「サイメル２７２」、「マイコート１０２」、「サイメル３２５」、「サイメル３２７」、「サイメル７０３」、「サイメル７１２」、「マイコート１０５」、「マイコート１０６」、「サイメル２６６」、「サイメル２６７」、「サイメル２８５」、「サイメル２３２」、「サイメル２３５」、「サイメル２３６」、「サイメル２３８」、「マイコート５０６」、「サイメル７０１」、「サイメル２７２」、「サイメル２１２」、「サイメル２５３」、「サイメル２５４」、「マイコート５０８」、「サイメル１１２８」、「マイコート１３０」、「サイメル２０２」、「サイメル２０７」（以上、サイテックインダストリーズ社製）、「ニカラックＭＷ－３０ＨＭ」、「ニカラックＭＷ３９０」、「ニカラックＭＸ－７５０」、「ニカラックＭＸ－７０６」（以上、三和ケミカル社製）等が挙げられる。 Specific examples of melamines include “Cymel 300”, “Cymel 301”, “Cymel 303”, “Cymel 350”, “Cymel 1123”, “Cymel 370”, “Cymel 771”, “Cymel 272”, “My "Coat 102", "Cymel 325", "Cymel 327", "Cymel 703", "Cymel 712", "My Coat 105", "My Coat 106", "Cymel 266", "Cymel 267", "Cymel 285" , “Cymel 232”, “Cymel 235”, “Cymel 236”, “Cymel 238”, “My Coat 506”, “Cymel 701”, “Cymel 272”, “Cymel 212”, “Cymel 253”, “Cymel 254” ”,“ My Coat 508 ”,“ Cymel 1128 ”,“ My Coat 130 ”, "Cymel 202", "Cymel 207" (manufactured by Cytec Industries, Inc.), "Nikarak MW-30HM", "Nikarak MW390", "Nikarak MX-750", "Nikarak MX-706" (above, manufactured by Sanwa Chemical Co., Ltd.) ) And the like.
　グリコールウリル類の具体例としては、「サイメル１１７０」、「サイメル１１７２」（以上、サイテックインダストリーズ社製）、「ニカラックＭＸ－２７０」（以上、三和ケミカル社製）等が挙げられる。 Specific examples of glycolurils include “Cymel 1170”, “Cymel 1172” (manufactured by Cytec Industries, Inc.), “Nicarac MX-270” (manufactured by Sanwa Chemical Co., Ltd.), and the like.
　エポキシ化合物の具体例としては、ジシクロペンタジエンを骨格とする３官能性のエポキシ化合物（商品名「ＸＤ－１０００」。日本化薬社製）、２，２－ビス（ヒドロキシメチル）１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物（シクロヘキサン骨格及び末端エポキシ基を有する１５官能性の脂環式エポキシ樹脂。商品名「ＥＨＰＥ３１５０」。ダイセル化学工業社製）、エポキシ化３－シクロヘキセン－１，２－ジカルボン酸ビス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン（脂肪族環状３官能性のエポキシ樹脂。商品名「エポリードＧＴ３０１」。ダイセル化学工業社製）、エポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン（脂肪族環状４官能性のエポキシ樹脂。商品名「エポリードＧＴ４０１」。ダイセル化学工業社製）、３，４－エポキシシクロヘキシルメチルアクリレート（商品名「サイクロマーＡ４００」、ダイセル化学工業社製）、１，２，８，９－ジエポキシリモネン（商品名「セロキサイド３０００」。ダイセル化学工業社製）、（３’，４’－エポキシシクロヘキサン）メチル３，４－エポキシシクロヘキサンカルボキシレート（商品名「セロキサイド２０２１」。ダイセル化学工業社製）、１，２－エポキシ－４－ビニルシクロヘキサン（商品名「セロキサイド２０００」。ダイセル化学工業社製）等の脂環構造を有するエポキシ化合物； Specific examples of the epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.) and 2,2-bis (hydroxymethyl) 1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150” manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin. Trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone ( Aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl acrylate (trade name “Cyclomer A400” manufactured by Daicel Chemical Industries, Ltd.), 1, 2,8,9-diepoxy limonene (trade name “Celoxide 3000” manufactured by Daicel Chemical Industries), (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate (trade name “Celoxide 2021”) Epoxy compounds having an alicyclic structure such as Daicel Chemical Industries, Ltd., 1,2-epoxy-4-vinylcyclohexane (trade name “Celoxide 2000”, manufactured by Daicel Chemical Industries, Ltd.);
芳香族アミン型多官能エポキシ化合物（商品名「Ｈ－４３４」、東都化成工業社製）、クレゾールノボラック型多官能エポキシ化合物（商品名「ＥＯＣＮ－１０２０」、日本化薬社製）、フェノールノボラック型多官能エポキシ化合物（エピコート１５２、１５４、ジャパンエポキシレジン社製）、ナフタレン骨格を有する多官能エポキシ化合物（商品名ＥＸＡ－４７００、大日本インキ化学株式会社製）、鎖状アルキル多官能エポキシ化合物（商品名「ＳＲ－ＴＭＰ」、阪本薬品工業株式会社製）、多官能エポキシポリブタジエン（商品名「エポリードＰＢ３６００」、ダイセル化学工業社製）、グリセリンのグリシジルポリエーテル化合物（商品名「ＳＲ－ＧＬＧ」、阪本薬品工業株式会社製）、ジグリセリンポリグリシジルエーテル化合物（商品名「ＳＲ－ＤＧＥ」、阪本薬品工業株式会社製）、ポリグリセリンポリグリシジルエーテル化合物（商品名「ＳＲ－４ＧＬ」、阪本薬品工業株式会社製）等の脂環構造を有さないエポキシ化合物；を挙げることができる。
　これらの中でも、エポキシ化合物が好ましく、脂環構造を有するエポキシ化合物が、本発明の樹脂組成物から得られる樹脂膜と基板との密着性を高くすることができるので、更に好ましい。 Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP” (Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”, Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto) Yakuhin Kogyo Co., Ltd.), diglycerin polyglycidyl etherification Epoxys that do not have an alicyclic structure such as products (trade name “SR-DGE”, manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyglycerin polyglycidyl ether compounds (trade name “SR-4GL”, manufactured by Sakamoto Pharmaceutical Co., Ltd.) A compound;
Among these, an epoxy compound is preferable, and an epoxy compound having an alicyclic structure is more preferable because adhesion between the resin film obtained from the resin composition of the present invention and the substrate can be increased.
　架橋剤（Ｆ）の分子量は、特に限定されないが、通常、１００～１００，０００、好ましくは５００～５０，０００、より好ましくは１，０００～１０，０００である。架橋剤は、それぞれ単独で又は２種以上を組み合わせて用いることができる。
　本発明の樹脂組成物における架橋剤（Ｆ）の含有量は、バインダー樹脂（Ａ）１００重量部に対して、通常、０．１～２００重量部、好ましくは１～１５０重量部、より好ましくは５～１００重量部の範囲である。架橋剤の使用量がこの範囲にあれば、十分な耐熱性が得られ、好ましい。 The molecular weight of the crosslinking agent (F) is not particularly limited, but is usually 100 to 100,000, preferably 500 to 50,000, and more preferably 1,000 to 10,000. A crosslinking agent can be used individually or in combination of 2 types or more, respectively.
The content of the crosslinking agent (F) in the resin composition of the present invention is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 100 parts by weight of the binder resin (A). It is in the range of 5 to 100 parts by weight. If the usage-amount of a crosslinking agent exists in this range, sufficient heat resistance will be acquired and it is preferable.
　その他の配合剤
　本発明の樹脂組成物は、本発明の効果が阻害されない範囲であれば、所望により、増感剤、界面活性剤、潜在的酸発生剤、酸化防止剤、光安定剤、消泡剤、顔料、染料等のその他の配合剤；等を含有していてもよい。 Other Compounding Agents The resin composition of the present invention may be a sensitizer, a surfactant, a latent acid generator, an antioxidant, a light stabilizer, a quenching agent, if desired, as long as the effects of the present invention are not impaired. Other compounding agents such as foaming agents, pigments, dyes and the like may be contained.
　増感剤の具体例としては、２Ｈ－ピリド－（３，２－ｂ）－１，４－オキサジン－３（４Ｈ）－オン類、１０Ｈ－ピリド－（３，２－ｂ）－１，４－ベンゾチアジン類、ウラゾール類、ヒダントイン類、バルビツール酸類、グリシン無水物類、１－ヒドロキシベンゾトリアゾール類、アロキサン類、マレイミド類等が挙げられる。 Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.
　本発明において、樹脂組成物の成分として、界面活性剤を含有することが好ましい。
　界面活性剤は、ストリエーション（塗布筋あと）の防止、現像性の向上等の目的で使用される。その具体例としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアリールエーテル類；ポリオキシエチレンジラウレート、ポリオキシエチレンジステアレート等のポリオキシエチレンジアルキルエステル類等のノニオン系界面活性剤；フッ素系界面活性剤；シリコーン系界面活性剤；メタクリル酸共重合体系界面活性剤；アクリル酸共重合体系界面活性剤；等が挙げられる。 In this invention, it is preferable to contain surfactant as a component of a resin composition.
The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer surfactants Agents; acrylic acid copolymer surfactants; and the like.
　潜在的酸発生剤は、本発明の樹脂組成物の耐熱性及び耐薬品性を向上する目的で使用される。その具体例としては、加熱により酸を発生するカチオン重合触媒である、スルホニウム塩、ベンゾチアゾリウム塩、アンモニウム塩、ホスホニウム塩等が挙げられる。これらの中でも、スルホニウム塩及びベンゾチアゾリウム塩が好ましい。 The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.
　酸化防止剤としては、通常の重合体に使用されている、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤、ラクトン系酸化防止剤等が使用できる。例えば、フェノール系酸化防止剤として、２，６－ジ－ｔ－ブチル－４－メチルフェノール、ｐ－メトキシフェノール、スチレン化フェノール、ｎ－オクタデシル－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、２，２’－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、２－ｔ－ブチル－６－（３’－ｔ－ブチル－５’－メチル－２’－ヒドロキシベンジル）－４－メチルフェニルアクリレート、４，４’－ブチリデン－ビス－（３－メチル－６－ｔ－ブチルフェノール）、４，４’－チオ－ビス（３－メチル－６－ｔ－ブチルフェノール）、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、アルキル化ビスフェノール等を挙げることができる。リン系酸化防止剤としては、亜リン酸トリフェニル、亜リン酸トリス（ノニルフェニル）等が挙げられる。イオウ系酸化防止剤としては、チオジプロピオン酸ジラウリル等が挙げられる。 As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as a phenolic antioxidant, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t- Butyl-4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl -2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6- t-butylphenol), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol, etc. It can be mentioned. Examples of phosphorus antioxidants include triphenyl phosphite and tris phosphite (nonylphenyl). Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.
　本発明において、樹脂組成物の成分として、光安定剤を含有することが好ましい。
　光安定剤は、ベンゾフェノン系、サリチル酸エステル系、ベンゾトリアゾール系、シアノアクリレート系、金属錯塩系等の紫外線吸収剤、ヒンダードアミン系（ＨＡＬＳ）等、光により発生するラジカルを捕捉するもの等のいずれでもよい。これらのなかでも、ＨＡＬＳはピペリジン構造を有する化合物で、本発明の組成物に対し着色が少なく、安定性がよいため好ましい。具体的な化合物としては、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、１，２，２，６，６－ペンタメチル－４－ピペリジル／トリデシル１，２，３，４－ブタンテトラカルボキシレート、ビス（１－オクチロキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート等が挙げられる。 In the present invention, it is preferable to contain a light stabilizer as a component of the resin composition.
The light stabilizer may be any of benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex-based and other ultraviolet absorbers, hindered amine-based (HALS), and the like that captures radicals generated by light. . Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
　樹脂組成物の調製方法
　本発明の樹脂組成物の調製方法は、特に限定されず、本発明の樹脂組成物の各構成成分、即ち、バインダー樹脂（Ａ）、酸性基を有する化合物（Ｂ）、ケイ素原子、チタン原子、アルミニウム原子、ジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）及び有機溶媒（Ｃ）、並びに所望により使用するその他の成分を公知の方法により混合すればよい。
　混合の方法は特に限定されないが、樹脂組成物の各構成成分を有機溶媒（Ｃ）に溶解又は分散して得られる溶液又は分散液を混合するのが好ましい。これにより、本発明の樹脂組成物は、溶液又は分散液の形態で得られる。 Preparation Method of Resin Composition The preparation method of the resin composition of the present invention is not particularly limited, and each component of the resin composition of the present invention, that is, the binder resin (A), the compound having an acidic group (B), Compound (D) and organic solvent (C) having one atom selected from silicon atom, titanium atom, aluminum atom and zirconium atom, and having hydrocarbyloxy group or hydroxy group bonded to the atom, and optionally What is necessary is just to mix the other component to be used by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component of the resin composition in the organic solvent (C). Thereby, the resin composition of this invention is obtained with the form of a solution or a dispersion liquid.
　本発明の樹脂組成物の各構成成分を有機溶媒（Ｃ）に溶解又は分散する方法は、常法に従えばよい。具体的には、攪拌子とマグネティックスターラーを使用して攪拌する方法や、高速ホモジナイザー、ディスパー、遊星攪拌機、二軸攪拌機、ボールミル、三本ロール等を使用する方法などが挙げられる。また、各成分を有機溶媒（Ｃ）に溶解又は分散した後に、例えば、孔径が０．５μｍ程度のフィルター等を用いて濾過してもよい。 The method for dissolving or dispersing each component of the resin composition of the present invention in the organic solvent (C) may be in accordance with a conventional method. Specific examples include a method of stirring using a stirrer and a magnetic stirrer, and a method of using a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a triple roll, and the like. Further, after each component is dissolved or dispersed in the organic solvent (C), it may be filtered using, for example, a filter having a pore size of about 0.5 μm.
　本発明の樹脂組成物の各構成成分を有機溶媒（Ｃ）に溶解又は分散するときの固形分濃度は、通常、１～７０重量％、好ましくは５～６０重量％、より好ましくは１０～５０重量％である。固形分濃度がこの範囲にあれば、溶解安定性、基板上への塗布性や形成される樹脂膜の膜厚均一性、平坦性等が高度にバランスされ得る。 The solid content concentration when each component of the resin composition of the present invention is dissolved or dispersed in the organic solvent (C) is usually 1 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50%. % By weight. If the solid content concentration is in this range, the dissolution stability, the coating property on the substrate, the film thickness uniformity of the formed resin film, the flatness, etc. can be highly balanced.
　積層体
　本発明の積層体は、本発明の樹脂組成物を用いて基板上に樹脂膜を形成させることによって得ることができる。 Laminate The laminate of the present invention can be obtained by forming a resin film on a substrate using the resin composition of the present invention.
　本発明において、基板は、例えば、プリント配線基板、シリコンウエハー基板、ガラス基板、プラスチック基板等を用いることができる。また、ディスプレイ分野において使用される、ガラス基板やプラスチック基板等に薄型トランジスタ型液晶表示素子、カラーフィルター、ブラックマトリックス等が形成されたものも好適に用いられる。 In the present invention, as the substrate, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.
　樹脂膜を基板上に形成する方法は、特に限定されず、例えば、塗布法やフィルム積層法等の方法を用いることができる。塗布法は、例えば、樹脂組成物を基板上に塗布した後、加熱乾燥して溶媒を除去する方法である。樹脂組成物を基板上に塗布する方法としては、例えば、スプレー法、スピンコート法、ロールコート法、ダイコート法、ドクターブレード法、回転塗布法、バー塗布法、スクリーン印刷法等の各種の方法を採用することができる。加熱乾燥条件は、各成分の種類や配合割合に応じて異なるが、加熱温度は、通常、３０～１５０℃、好ましくは６０～１２０℃であり、加熱時間は、通常、０．５～９０分間、好ましくは１～６０分間、より好ましくは１～３０分間である。 The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The coating method is, for example, a method of removing a solvent by applying a resin composition on a substrate and then drying by heating. Examples of the method for applying the resin composition on the substrate include various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. Can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., preferably 60 to 120 ° C., and the heating time is usually 0.5 to 90 minutes. It is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
　前記フィルム積層法は、樹脂組成物を、樹脂フィルムや金属フィルム等のＢステージフィルム形成用基材上に塗布した後に加熱乾燥により溶媒を除去してＢステージフィルムを得、次いで、このＢステージフィルムを前記基材上に積層する方法である。加熱乾燥条件は、各成分の種類や配合割合に応じて適宜選択することができるが、加熱温度は、通常、３０～１５０℃であり、加熱時間は、通常、０．５～９０分間である。フィルム積層は、加圧ラミネータ、プレス、真空ラミネータ、真空プレス、ロールラミネータ等の圧着機を用いて行なうことができる。 In the film laminating method, the resin composition is applied on a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film. Is laminated on the substrate. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.
　基板上に形成された樹脂膜の厚さは、通常、０．１～１００μｍ、好ましくは０．５～５０μｍ、より好ましくは０．５～３０μｍである。 The thickness of the resin film formed on the substrate is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.
　本発明において、基板上に樹脂膜を形成した後に、樹脂の架橋反応を行なうことができる。
　基板上に形成された樹脂膜の架橋は、架橋剤の種類に応じて適宜方法を選択すればよいが、通常、加熱により行なう。加熱方法は、例えば、ホットプレート、オーブン等を用いて行なうことができる。加熱温度は、通常、１８０～２５０℃であり、加熱時間は、樹脂膜の大きさや厚さ及び使用機器等により適宜選択され、例えばホットプレートを用いる場合は、通常、５～６０分間、オーブンを用いる場合は、通常、３０～９０分間の範囲である。加熱は、必要に応じて不活性ガス雰囲気下で行ってもよい。不活性ガスとしては、酸素を含まず且つ樹脂膜を酸化させないものであればよく、例えば、窒素、アルゴン、ヘリウム、ネオン、キセノン、クリプトン等が挙げられる。これらの中でも窒素とアルゴンが好ましく、特に窒素が好ましい。特に、酸素含有量が０．１体積％以下、好ましくは０．０１体積％以下の不活性ガス、特に窒素が好適である。これらの不活性ガスは、それぞれ単独で又は２種以上を組み合わせて用いることができる。 In the present invention, after the resin film is formed on the substrate, a resin crosslinking reaction can be performed.
Crosslinking of the resin film formed on the substrate may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, the oven is usually run for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. The inert gas is not particularly limited as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.
　基板と基板上に本発明の樹脂組成物を用いて形成した樹脂膜とからなる積層体において、樹脂膜はパターン化され、パターン化樹脂膜とされていてもよい。
　基板上に形成されたパターン化樹脂膜は、例えば、樹脂膜に活性放射線を照射して潜像パターンを形成し、次いで潜像パターンを有する樹脂膜に現像液を接触させることによりパターンを顕在化させて得ることができる。 In a laminate composed of a substrate and a resin film formed on the substrate using the resin composition of the present invention, the resin film may be patterned to form a patterned resin film.
The patterned resin film formed on the substrate, for example, exposes the resin film to actinic radiation to form a latent image pattern, and then exposes the developer film to the resin film having the latent image pattern to reveal the pattern. Can be obtained.
　パターン化樹脂膜を形成する際には、まず、基板上に形成された樹脂膜に活性放射線を照射して潜像パターンを形成する。活性放射線としては、光酸発生剤を活性化させ、光酸発生剤を含む架橋性組成物のアルカリ可溶性を変化させることができるものであれば特に限定されない。具体的には、紫外線、ｇ線やｉ線等の単一波長の紫外線、ＫｒＦエキシマレーザー光、ＡｒＦエキシマレーザー光等の光線；電子線のような粒子線；等を用いることができる。これらの活性放射線を選択的にパターン状に照射して潜像パターンを形成する方法としては、常法に従えばよく、例えば、縮小投影露光装置等により、紫外線、ｇ線、ｉ線、ＫｒＦエキシマレーザー光、ＡｒＦエキシマレーザー光等の光線を所望のマスクパターンを介して照射する方法、又は電子線等の粒子線により描画する方法等を用いることができる。活性放射線として光線を用いる場合は、単一波長光であっても、混合波長光であってもよい。照射条件は、使用する活性放射線に応じて適宜選択されるが、例えば、波長２００～４５０ｎｍの光線を使用する場合、照射量は、通常１０～１，０００ｍＪ／ｃｍ２、好ましくは５０～５００ｍＪ／ｃｍ２の範囲であり、照射時間と照度に応じて決まる。このようにして活性放射線を照射した後、必要に応じ、樹脂膜を６０～１３０℃程度の温度で１～２分間程度加熱処理する。 When forming the patterned resin film, first, a latent image pattern is formed by irradiating the resin film formed on the substrate with active radiation. The actinic radiation is not particularly limited as long as it can activate the photoacid generator and change the alkali solubility of the crosslinkable composition containing the photoacid generator. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be followed. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions are appropriately selected depending on the actinic radiation to be used. For example, when a light beam having a wavelength of 200 to 450 nm is used, the irradiation amount is usually 10 to 1,000 mJ / cm 2 , preferably 50 to 500 mJ / cm 2 . It is a range of cm 2 and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.
　次に、樹脂膜に形成された潜像パターンを現像して顕在化させる。本発明では、このような工程を「パターン化」といい、パターン化された樹脂膜を「パターン化樹脂膜」という。現像液としては、通常、アルカリ性化合物の水性溶液が用いられる。アルカリ性化合物としては、例えば、アルカリ金属塩、アミン、アンモニウム塩を使用することができる。アルカリ性化合物は、無機化合物であっても有機化合物であってもよい。これらの化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム等のアルカリ金属塩；アンモニア水；エチルアミン、ｎ－プロピルアミン等の第一級アミン；ジエチルアミン、ジ－ｎ－プロピルアミン等の第二級アミン；トリエチルアミン、メチルジエチルアミン等の第三級アミン；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、コリン等の第四級アンモニウム塩；ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン；ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン、Ｎ－メチルピロリドン等の環状アミン類；等が挙げられる。これらアルカリ性化合物は、それぞれ単独で又は２種以上を組み合わせて用いることができる。 Next, the latent image pattern formed on the resin film is developed and made visible. In the present invention, such a process is called “patterning”, and the patterned resin film is called “patterned resin film”. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.
　アルカリ水性溶液の水性媒体としては、水；メタノール、エタノール等の水溶性有機溶媒；を使用することができる。アルカリ水性溶液は、界面活性剤等を適当量添加したものであってもよい。
　潜像パターンを有する樹脂膜に現像液を接触させる方法としては、例えば、パドル法、スプレー法、ディッピング法等の方法が用いられる。現像条件としては、適宜選択すればよいが、現像温度は、通常、０～１００℃、好ましくは５～５５℃、より好ましくは１０～３０℃の範囲であり、現像時間は、通常、３０～１８０秒間の範囲である。 As the aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development conditions may be appropriately selected. The development temperature is usually in the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and the development time is usually 30 to 30 ° C. The range is 180 seconds.
　このようにして目的とするパターン化樹脂膜を基板上に形成した後、必要に応じて、基板上、基板裏面及び基板端部の現像残渣を除去するために、基板をリンス液でリンスすることができる。リンス処理の後、残存しているリンス液を圧縮空気や圧縮窒素により除去する。
　更に、必要に応じて、光酸発生剤を失活させるために、パターン化樹脂膜を有する基板全面に活性放射線を照射することもできる。活性放射線の照射には、上記潜像パターンの形成方法において例示した方法を利用できる。活性放射線の照射と同時に又は照射後に樹脂膜を加熱してもよい。加熱方法としては、例えば、基板をホットプレートやオーブン内で加熱する方法が挙げられる。温度は、通常、１００～３００℃、好ましくは１２０～２００℃の範囲である。 After the desired patterned resin film is formed on the substrate in this way, the substrate is rinsed with a rinsing solution in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate, if necessary. Can do. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Further, if necessary, the entire surface of the substrate having the patterned resin film can be irradiated with actinic radiation in order to deactivate the photoacid generator. For irradiation with actinic radiation, the method exemplified in the method for forming a latent image pattern can be used. You may heat a resin film simultaneously with irradiation of actinic radiation, or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.
　本発明において、基板上にパターン化樹脂を形成した後に、パターン化樹脂の架橋反応を行なうことができる。
　架橋は、上述した基板上に形成された樹脂膜の架橋と同様に行なえばよい。 In this invention, after forming patterned resin on a board | substrate, the crosslinking reaction of patterned resin can be performed.
The crosslinking may be performed in the same manner as the above-described crosslinking of the resin film formed on the substrate.
　本発明の積層体、特に基板上にパターン化樹脂膜を形成した積層体は、種々の電子部品、特に半導体デバイスとして有用である。 The laminate of the present invention, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components, particularly semiconductor devices.
　以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
　なお、本実施例において、「部」及び「％」は、特に断りのない限り、それぞれ、「重量部」及び「重量％」である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In this example, “parts” and “%” are “parts by weight” and “% by weight”, respectively, unless otherwise specified.
　各特性は、以下の方法により評価した。
（１）重合転化率
　重合転化率は、ガスクロマトグラフィーにより、残留単量体量を測定し、その測定値から算出した。
（２）重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）
　テトラヒドロフランを溶離液とするゲルパーミエーションクロマトグラフィーにより、ポリスチレン換算値として測定した。
（３）水素化率
　水素化率は、１Ｈ－ＮＭＲにより測定し、水素添加前の炭素－炭素二重結合モル数に対する、水素化された炭素－炭素二重結合モル数の水素添加前の割合として、その測定値から算出した。
（４）密着性
〔測定用試料の作製〕
　ガラス基板［コーニング社、コーニング１７３７（製品名）］上に、各実施例、比較例にて得られた樹脂組成物をスピンコートしたのち、ホットプレートを用いて９０℃で２分間プリベークして、膜厚２．５μｍの樹脂膜を形成した。この樹脂膜に所定パターンを有するマスクを介して３６５ｎｍにおける光強度が５ｍＷ／ｃｍ２である紫外線を、４０秒間空気中で照射した。
　次いで、０．４重量％テトラメチルアンモニウムヒドロキシド水溶液を用いて、２５℃で６０秒間現像処理を行ったのち、超純水で３０秒間リンスして、パターンを形成した。
　さらに、オーブンを用いて、２３０℃で６０分間加熱するポストベークを行い、密着性測定用の積層体を得た。
〔密着性の測定〕
　得られた積層体について、コーテック社製のアドヒージョンテスターを用いてプルオフ法による測定を行なった。測定の結果に基づいて下記の基準で、得られた積層体の密着性を判定する。
　◎：８ＭＰａ以上
　○：５ＭＰａ以上８ＭＰａ未満
　△：３ＭＰａ以上５ＭＰａ未満
　×：３ＭＰａ未満 Each characteristic was evaluated by the following methods.
(1) Polymerization conversion rate The polymerization conversion rate was calculated from the measured value by measuring the amount of residual monomer by gas chromatography.
(2) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
It was measured as a polystyrene equivalent value by gel permeation chromatography using tetrahydrofuran as an eluent.
(3) Hydrogenation rate The hydrogenation rate was measured by 1 H-NMR, and the hydrogenated carbon-carbon double bond moles before hydrogenation relative to the carbon-carbon double bond moles before hydrogenation. The ratio was calculated from the measured value.
(4) Adhesion [Preparation of measurement sample]
After spin-coating the resin composition obtained in each example and comparative example on a glass substrate [Corning, Corning 1737 (product name)], prebaking at 90 ° C. for 2 minutes using a hot plate, A resin film having a thickness of 2.5 μm was formed. The resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm 2 in the air for 40 seconds through a mask having a predetermined pattern.
Next, a development process was performed at 25 ° C. for 60 seconds using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing with ultrapure water for 30 seconds to form a pattern.
Furthermore, the post-baking heated for 60 minutes at 230 degreeC was performed using oven, and the laminated body for adhesiveness measurement was obtained.
[Measurement of adhesion]
About the obtained laminated body, the measurement by the pull-off method was performed using the adhesion tester by a Co-Tech company. Based on the measurement results, the adhesion of the obtained laminate is determined according to the following criteria.
◎: 8 MPa or more ○: 5 MPa or more and less than 8 MPa Δ: 3 MPa or more and less than 5 MPa ×: Less than 3 MPa
〔製造例１〕
（アクリル樹脂の製造）
　スチレン２０部、ブチルメタクリレート２５部、２－エチルヘキシルアクリレート２５部、メタクリル酸３０部、２，２－アゾビスイソブチロニトリル０．５部、及びプロピレングリコールモノメチルエーテルアセテート３００部を窒素気流中で撹拌しながら８０℃で５時間加熱した。得られた樹脂溶液をロータリーエバポレーターで濃縮し、固形分濃度３５％のアクリル樹脂溶液を得た。 [Production Example 1]
(Manufacture of acrylic resin)
20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 part of 2,2-azobisisobutyronitrile and 300 parts of propylene glycol monomethyl ether acetate are stirred in a nitrogen stream. The mixture was heated at 80 ° C. for 5 hours. The obtained resin solution was concentrated by a rotary evaporator to obtain an acrylic resin solution having a solid content concentration of 35%.
〔製造例２〕
（プロトン性極性基を有する環状オレフィン重合体の製造）
　プロトン性極性基を有する環状オレフィン単量体として９－ヒドロキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン６０部、プロトン性極性基を有さない環状オレフィン単量体としてテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン（「テトラシクロドデセン」ともいう。）４０部、１，５－ヘキサジエン２．８部、（１，３－ジメシチルイミダゾリジン－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド０．０５部及びジエチレングリコールエチルメチルエーテル４００部を、窒素置換した耐圧ガラス反応器に仕込み、撹拌下に８０℃で２時間重合反応を行って開環メタセシス重合体１Ａを含有する重合反応溶液を得た。重合転化率は、９９．９％以上であった。この重合体１Ａの重量平均分子量は３，２００、数平均分子量は１，９００、分子量分布は１．６８であった。 [Production Example 2]
(Production of cyclic olefin polymer having a protic polar group)
As a cyclic olefin monomer having a protic polar group, 9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 60 parts, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”) 40 parts, 1,5-hexadiene 2.8 parts, (1,3-dimesitylimidazolidine-2-ylidene) ( Tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol ethyl methyl ether 400 part were charged into a nitrogen-substituted pressure-resistant glass reactor, and the polymerization reaction was carried out at 80 ° C. for 2 hours with stirring to obtain a ring-opening metathesis polymer 1A. A polymerization reaction solution was obtained. The polymerization conversion rate was 99.9% or more. The polymer 1A had a weight average molecular weight of 3,200, a number average molecular weight of 1,900, and a molecular weight distribution of 1.68.
　次いで、水素添加触媒としてビス（トリシクロヘキシルホスフィン）エトキシメチレンルテニウムジクロリド０．１部を、上記にて得られた重合反応溶液に加え、水素を４ＭＰａの圧力で５時間溶存させて、水素添加反応を進行させた。その後、この溶液に、活性炭粉末１部を添加し、これをオートクレーブに入れて、撹拌しつつ１５０℃で水素を４ＭＰａの圧力で３時間溶存させた。次いで、得られた溶液を取り出して、孔径０．２μｍのフッ素樹脂製フィルターで溶液をろ過して活性炭を分離して、開環メタセシス重合体１Ａの水素化物１Ｂを含有する水素添加反応溶液４７６部を得た。ろ過は、滞りなく行なうことができた。ここで得られた水素化物１Ｂを含有する水素添加反応溶液の固形分濃度は２０．６％であり、水素化物１Ｂの収量は９８．１部であった。得られた水素化物１Ｂの重量平均分子量は４，４３０、数平均分子量は２，５７０、分子量分布は１．７２であった。水素化率は９９．９％であった。 Next, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst is added to the polymerization reaction solution obtained above, and hydrogen is dissolved at a pressure of 4 MPa for 5 hours to carry out the hydrogenation reaction. Proceeded. Thereafter, 1 part of activated carbon powder was added to this solution, and this was put into an autoclave, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring. Next, the obtained solution was taken out, the solution was filtered with a fluororesin filter having a pore size of 0.2 μm to separate activated carbon, and 476 parts of hydrogenation reaction solution containing hydride 1B of ring-opening metathesis polymer 1A. Got. Filtration could be performed without any delay. The hydrogenation reaction solution containing hydride 1B obtained here had a solid content concentration of 20.6%, and the yield of hydride 1B was 98.1 parts. The obtained hydride 1B had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, and a molecular weight distribution of 1.72. The hydrogenation rate was 99.9%.
　得られた水素化物１Ｂの水素添加反応溶液をロータリーエバポレーターで濃縮し、固形分濃度を３５％に調整して、水素化物１Ｃ（プロトン性極性基としてカルボキシ基を有する環状オレフィン重合体）の溶液を得た。濃縮の前後で収量、水素化物の重量平均分子量、数平均分子量、及び分子量分布に変化はなかった。 The obtained hydrogenation reaction solution of hydride 1B was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride 1C (a cyclic olefin polymer having a carboxy group as a protic polar group) was prepared. Obtained. There was no change in yield, hydride weight average molecular weight, number average molecular weight, and molecular weight distribution before and after concentration.
〔製造例３〕
（カルド樹脂の製造）
　還留冷却器付き四つ口フラスコ中にビスフェノールフルオレン型エポキシ樹脂とアクリル酸との等当量反応物（固形分濃度５０％、固形分換算の酸価１．２８ｍｇＫＯＨ／ｇ、エポキシ当量２１，３００。新日鐵化学社製、製品名「ＡＳＦ－４００」溶液）の５０％プロピレングリコールモノメチルエーテルアセテート溶液１９８．５３部と、ベンゾフェノンテトラカルボン酸二無水物３９．５４部、コハク酸無水物８．１３部、プロピレングリコールモノメチルエーテルアセテート４８．１２部及びトリフェニルホスフィン０．４５部を仕込み、１２０～１２５℃の加熱下にて１ｈｒ撹拌し、更に７５～８０℃で６ｈｒの加熱撹拌を行い、その後、グリシジルメタクリレート８．６部を投入し、更に８０℃で８時間攪拌した。得られた樹脂溶液をロータリーエバポレーターで濃縮し、固形分濃度３５％のカルド樹脂溶液を得た。 [Production Example 3]
(Manufacture of cardo resin)
Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid in a four-necked flask with a reflux condenser (solid content concentration 50%, acid value 1.28 mgKOH / g in terms of solid content, epoxy equivalent 21,300. 198.53 parts of 50% propylene glycol monomethyl ether acetate solution manufactured by Nippon Steel Chemical Co., Ltd., product name “ASF-400” solution, 39.54 parts of benzophenone tetracarboxylic dianhydride, 8.13 of succinic anhydride Part, 48.12 parts of propylene glycol monomethyl ether acetate and 0.45 part of triphenylphosphine, stirred for 1 hour under heating at 120 to 125 ° C., and further for 6 hours at 75 to 80 ° C. 8.6 parts of glycidyl methacrylate was added and further stirred at 80 ° C. for 8 hours. The obtained resin solution was concentrated by a rotary evaporator to obtain a cardo resin solution having a solid concentration of 35%.
〔製造例４〕
（ポリシロキサンの製造）
　三口フラスコにメチルトリメトキシシラン７４．９１部，フェニルトリメトキシシラン６９．４１部、及びジアセトンアルコール（ＤＡＡ）１５０．３６部を仕込み、室温で攪拌しながら水５５．８部にリン酸０．３３８部（仕込みモノマーに対して０．２重量％）を溶かしたリン酸水溶液を１０分かけて添加した。その後、フラスコを７０℃のオイルバスに漬けて１時間攪拌した後、オイルバスを３０分かけて１１５℃まで昇温した。昇温開始１時間後に溶液の内温が１００℃に到達し、そこから２時間加熱攪拌した（内温は１００～１１０℃）。副生成物であるメタノール、水を合計１１５部留出した。得られたポリシロキサンのＤＡＡ溶液に、固形分濃度が３５重量％となるようにＤＡＡを加えてポリシロキサン溶液を得た。 [Production Example 4]
(Manufacture of polysiloxane)
A three-necked flask was charged with 74.91 parts of methyltrimethoxysilane, 69.41 parts of phenyltrimethoxysilane, and 150.36 parts of diacetone alcohol (DAA), and 0. 5 parts of water was added to 55.8 parts of water while stirring at room temperature. An aqueous phosphoric acid solution in which 338 parts (0.2% by weight based on the charged monomers) had been dissolved was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.). A total of 115 parts of methanol and water as by-products were distilled off. DAA was added to the obtained polysiloxane DAA solution so that the solid concentration was 35% by weight to obtain a polysiloxane solution.
〔製造例５〕
（ポリイミドの製造）
　乾燥空気気流下、４つ口フラスコ内で４，４’－ジアミノジフェニルエーテル９．６１部、ビス［４－（４－アミノフェノキシ）フェニル］スルホン１７．３部、ビス（３－アミノプロピル）テトラメチルジシロキサン１．２４部及びシクロペンタノン１０２．５部を仕込み、４０℃で溶解させた。その後、無水ピロメリット酸６．５４部、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物９．６７部、３，３’，４，４’－ジフェニルエーテルテトラカルボン酸二無水物１２．４１部及びシクロペンタノン３０部を加え、５０℃で３時間反応させた。この溶液をロータリーエバポレーターで濃縮し、固形分濃度３５％のポリイミド溶液を得た。 [Production Example 5]
(Production of polyimide)
In a four-necked flask under a dry air stream, 9.61 parts of 4,4′-diaminodiphenyl ether, 17.3 parts of bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminopropyl) tetramethyl 1.24 parts of disiloxane and 102.5 parts of cyclopentanone were charged and dissolved at 40 ° C. Thereafter, pyromellitic anhydride 6.54 parts, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 9.67 parts, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 12.41 parts and 30 parts of cyclopentanone were added and reacted at 50 ° C. for 3 hours. This solution was concentrated by a rotary evaporator to obtain a polyimide solution having a solid concentration of 35%.
〔製造例６〕
（プロトン性極性基を有さない環状オレフィン重合体の製造））
　製造例２において、環状オレフィン単量体として、９－ヒドロキシカルボニルテトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン６０部、テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン４０部のかわりに、テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エン１００部とした他は、製造例２と同様に開環重合及び水素化を行って、テトラシクロ［６．２．１．１３，６．０２，７］ドデカ－４－エンの開環重合体水素化物（プロトン性極性基を有さない環状オレフィン重合体）の溶液を得た。 [Production Example 6]
(Production of cyclic olefin polymer having no protic polar group)
In Production Example 2, as the cyclic olefin monomer, 9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 60 parts tetracyclo [6.2.1.1 3,6 . Instead of 40 parts of 0 2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodeca-4-ene was used, except that ring-opening polymerization and hydrogenation were carried out in the same manner as in Production Example 2 to obtain tetracyclo [6.2.1.1 3,6 . A solution of a ring opening polymer hydride of 0 2,7 ] dodec-4-ene (a cyclic olefin polymer having no protic polar group) was obtained.
〔実施例１〕
　バインダー樹脂（Ａ）として、製造例１で得られたアクリル樹脂溶液１００部（ただし、固形分換算）、感放射線化合物（Ｅ）として、１，１，３－トリス（２，５－ジメチル－４－ヒドロキシフェニル）－３－フェニルプロパン（１モル）と１，２－ナフトキノンジアジド－５－スルホン酸クロライド（２．５モル）との縮合物（東洋合成社製、「ＴＳ２００（製品名）」）２５部、酸性基を有する化合物（Ｂ）として、２－（カルボキシメチル）安息香酸２０部、有機溶媒（Ｃ）として、ジエチレングリコールエチルメチルエーテル９２部及びＮ－メチル－２－ピロリドン８部、化合物（Ｄ）として、３－メルカプトプロピルトリメトキシシラン１０部、架橋剤（Ｆ）として、エポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン（脂肪族環状４官能性のエポキシ樹脂、商品名「エポリードＧＴ４０１」、ダイセル化学工業社製）２０部、老化防止剤として、（１，２，２，６，６－ペンタメチル－４－ピペリジル／トリデシル）－１，２，３，４－ブタンテトラカルボキシレート５部、ならびに、シリコーン系界面活性剤（製品名「ＫＰ３４１」、信越化学工業社製）０．０５部、を配合して混合撹拌した。
　３０分攪拌後、混合物は、均一な溶液になった。この溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して、樹脂組成物１Ｄを調製した。 [Example 1]
As binder resin (A), 100 parts of the acrylic resin solution obtained in Production Example 1 (in terms of solid content), and as radiation sensitive compound (E), 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) (Toyo Gosei Co., Ltd., “TS200 (product name)”) 25 parts, 20 parts of 2- (carboxymethyl) benzoic acid as compound (B) having an acidic group, 92 parts of diethylene glycol ethyl methyl ether and 8 parts of N-methyl-2-pyrrolidone as the organic solvent (C), compound ( D) as 10 parts of 3-mercaptopropyltrimethoxysilane and as crosslinking agent (F) epoxidized butanetetracarboxylic acid tetrakis (3-cyclo (Xenylmethyl) -modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.) 20 parts, (1,2,2,6,6-pentamethyl) as an anti-aging agent -4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate 5 parts, and silicone surfactant (product name “KP341”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 part And stirred.
After stirring for 30 minutes, the mixture became a homogeneous solution. This solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a resin composition 1D.
　次いで、この樹脂組成物１Ｄを用いて、上記方法に従い積層体を得、その密着性を評価した。結果を、表１に示す。
　なお、表１～７において、バインダー樹脂（Ａ）の配合量は、いずれも固形分換算で１００部という意味である。 Next, using this resin composition 1D, a laminate was obtained according to the above method, and the adhesion was evaluated. The results are shown in Table 1.
In Tables 1 to 7, the blending amount of the binder resin (A) means 100 parts in terms of solid content.
〔実施例２～７〕
　実施例１において、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表１に示す種類の化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの添加量を表１に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。
　結果を表１に示す。 [Examples 2 to 7]
In Example 1, the compound (B), the compound (D), and the crosslinking agent (F) shown in Table 1 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively. A resin composition was prepared in the same manner as in Example 1 except that the amount was changed to the amount shown in Table 1. Then, a laminate was obtained, and the adhesiveness of the obtained laminate was evaluated.
The results are shown in Table 1.
〔実施例８～１４〕
　実施例１において、バインダー樹脂（Ａ）として製造例２で得られた環状オレフィン重合体を用い、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表１～２に示す種類の化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの添加量を表１～２に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。
　結果を表１～２に示す。 [Examples 8 to 14]
In Example 1, the cyclic olefin polymer obtained in Production Example 2 was used as the binder resin (A), and the compounds (B), (D), and crosslinking agents (F) shown in Tables 1 and 2, respectively. A resin composition was prepared in the same manner as in Example 1, except that the compound (B), the compound (D), and the crosslinking agent (F) were added in the amounts shown in Tables 1 and 2. Subsequently, the laminated body was obtained and adhesiveness was evaluated about the obtained laminated body.
The results are shown in Tables 1-2.
〔実施例１５～２１〕
　実施例１において、バインダー樹脂（Ａ）として製造例３で得られたカルド樹脂を用い、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表２～３に示す種類の化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの添加量を表２～３に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。
　結果を表２～３に示す。 [Examples 15 to 21]
In Example 1, the cardo resin obtained in Production Example 3 was used as the binder resin (A), and the compounds shown in Tables 2 to 3 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively. A resin composition was prepared in the same manner as in Example 1 except that (B), compound (D) and crosslinking agent (F) were used, and the addition amounts thereof were as shown in Tables 2 to 3. A body was obtained, and adhesion was evaluated for the obtained laminate.
The results are shown in Tables 2-3.
〔実施例２２～２８〕
　実施例１において、バインダー樹脂（Ａ）として製造例４で得られたポリシロキサンを用い、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表３～４に示す種類の化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの添加量を表３～４に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。
　結果を表３～４に示す。 [Examples 22 to 28]
In Example 1, the polysiloxane obtained in Production Example 4 was used as the binder resin (A), and the compounds shown in Tables 3 to 4 were used as the compound (B), the compound (D), and the crosslinking agent (F), respectively. A resin composition was prepared in the same manner as in Example 1 except that (B), compound (D) and crosslinking agent (F) were used, and the addition amounts thereof were as shown in Tables 3 to 4. A body was obtained, and adhesion was evaluated for the obtained laminate.
The results are shown in Tables 3-4.
〔実施例２９～３５〕
　実施例１において、バインダー樹脂（Ａ）として製造例５で得られたポリイミドを用い、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表４～５に示す種類の化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの配合量を表４～５に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。
　結果を表４～５に示す。 [Examples 29 to 35]
In Example 1, the polyimide obtained in Production Example 5 was used as the binder resin (A), and the compounds (B), the compound (D), and the crosslinking agent (F) were each of the types of compounds shown in Tables 4 to 5 ( B), a resin composition was prepared in the same manner as in Example 1 except that the compound (D) and the crosslinking agent (F) were used, and the blending amounts thereof were as shown in Tables 4 to 5. The adhesion of the obtained laminate was evaluated.
The results are shown in Tables 4-5.
〔実施例３６～４６〕
　実施例１において、バインダー樹脂（Ａ）、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）として、それぞれ表５～６に示す種類のバインダー樹脂（Ａ）、化合物（Ｂ）、化合物（Ｄ）及び架橋剤（Ｆ）を用い、これらの配合量を表５～６に示す量とした他は、実施例１と同様にして樹脂組成物を調製し、次いで積層体を得、得られた積層体について密着性を評価した。なお、実施例４６において使用したバインダー樹脂（Ａ）は、製造例６で得られたプロトン性極性基を有しない環状オレフィン重合体を用いた。
　結果を表５～６に示す。 [Examples 36 to 46]
In Example 1, as binder resin (A), compound (B), compound (D) and crosslinking agent (F), binder resins (A), compound (B) and compound ( A resin composition was prepared in the same manner as in Example 1 except that D) and the crosslinking agent (F) were used, and the blending amounts thereof were those shown in Tables 5 to 6, and then a laminate was obtained. The adhesion was evaluated for the laminated body. As the binder resin (A) used in Example 46, the cyclic olefin polymer having no protic polar group obtained in Production Example 6 was used.
The results are shown in Tables 5-6.
〔比較例１、２〕
　化合物（Ｂ）と化合物（Ｄ）の添加量を、表７に示す量に変更した以外は実施例１と同様にして、各樹脂組成物を調製し、次いで積層体を得、得られた積層体について、密着性を評価した。
　結果を、表７に示す。 [Comparative Examples 1 and 2]
Each resin composition was prepared in the same manner as in Example 1 except that the addition amounts of the compound (B) and the compound (D) were changed to the amounts shown in Table 7, and then a laminate was obtained. The body was evaluated for adhesion.
The results are shown in Table 7.
〔比較例３、４〕
　化合物（Ｂ）、化合物（Ｄ）として、表７に示す、１種類の化合物（Ｂ）、１種類の化合物（Ｄ）のみを、それぞれ使用したこと以外は実施例１と同様にして、各樹脂組成物を調製し、次いで積層体を得、得られた積層体について、密着性を評価した。
　結果を、表７に示す。 [Comparative Examples 3 and 4]
As compound (B) and compound (D), each resin was used in the same manner as in Example 1 except that only one compound (B) and one compound (D) shown in Table 7 were used. A composition was prepared, a laminate was then obtained, and the adhesion of the obtained laminate was evaluated.
The results are shown in Table 7.
〔比較例５〕
　化合物（Ｂ）、化合物（Ｄ）を共に使用しなかったこと以外は実施例１と同様にして、樹脂組成物を調製し、次いで積層体を得、得られた積層体について、密着性を評価した。
　結果を、表７に示す。 [Comparative Example 5]
A resin composition was prepared in the same manner as in Example 1 except that neither the compound (B) nor the compound (D) was used. Then, a laminate was obtained, and the adhesiveness of the obtained laminate was evaluated. did.
The results are shown in Table 7.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　なお、表１～７において、実施例及び比較例で用いた化合物（Ｂ）の酸性基の数、酸解離定数（ｐＫａ又はｐＫａ１）は以下のとおりである。
・１，２－シクロヘキサンジカルボン酸：酸性基数２、ｐＫａ１は約４．８７
・アジピン酸：酸性基数２、ｐＫａ１は４．２６
・安息香酸：酸性基数１、ｐＫａは４～４．２
・フタル酸：酸性基数２、ｐＫａ１は２．９５
・２－（カルボキシメチル）安息香酸：酸性基数２、ｐＫａ１は４～４．５
ピラジン－２，３－ジカルボン酸：酸性基数２、ｐＫａ１は２．９５以下
２，４，６－トリメルカプト－ｓ－トリアジン：酸性基数３、ｐＫａ１は２．５
５－メルカプト－１，３，４－チアジアゾール－２－イルチオ）酢酸：酸性基数２、ｐＫａ１は２．７
　また、表１～７において、実施例及び比較例で用いた架橋剤（Ｆ）は以下のとおりである。
・ＳＲ－４ＧＬ：ポリグリセリンポリグリシジルエーテル化合物（商品名「ＳＲ－４ＧＬ」、阪本薬品工業株式会社製）
・ＧＴ４０１：エポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン（脂肪族環状４官能性のエポキシ樹脂。商品名「エポリードＧＴ４０１」。ダイセル化学工業社製） In Tables 1 to 7, the number of acidic groups and the acid dissociation constant (pKa or pKa1) of the compound (B) used in Examples and Comparative Examples are as follows.
1,2-cyclohexanedicarboxylic acid: 2 acidic groups, pKa1 is about 4.87
Adipic acid: 2 acidic groups, pKa1 is 4.26
Benzoic acid: 1 acidic group, pKa of 4 to 4.2
・ Phthalic acid: 2 acidic groups, pKa1 is 2.95
2- (carboxymethyl) benzoic acid: 2 acidic groups, pKa1 is 4 to 4.5
Pyrazine-2,3-dicarboxylic acid: Number of acidic groups 2, pKa1 is 2.95 or less 2,4,6-trimercapto-s-triazine: Number of acidic groups 3, pKa1 is 2.5
5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid: acid group number 2, pKa1 is 2.7
In Tables 1 to 7, the crosslinking agents (F) used in Examples and Comparative Examples are as follows.
SR-4GL: polyglycerin polyglycidyl ether compound (trade name “SR-4GL”, manufactured by Sakamoto Pharmaceutical Co., Ltd.)
GT401: epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.)
　表１～７の結果より、バインダー樹脂（Ａ）、酸性基を有する化合物（Ｂ）、有機溶媒（Ｃ）、並びにケイ素原子、チタン原子、アルミニウム原子、ジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を含有してなり、酸性基を有する化合物（Ｂ）が、脂肪族化合物、芳香族化合物、及び複素環化合物からなる群より選ばれた少なくとも１種であり、化合物（Ｂ）と化合物（Ｄ）の合計含有量がバインダー樹脂（Ａ）１００重量部に対して１０～５０の範囲である実施例１～４６の樹脂組成物を用いて基板上に樹脂膜を形成すると、得られた樹脂膜の基板に対する密着性が高い。
　これに対して、化合物（Ｂ）と化合物（Ｄ）の合計含有量が本発明で規定する範囲外である比較例１及び２の場合や、本発明で規定する化合物（Ｂ）及び化合物（Ｄ）のうちどちらか１種しか使用していない比較例３及び４の場合や、化合物（Ｂ）及び化合物（Ｄ）をどちらも使用していない比較例５の場合には、樹脂膜の基板に対する密着性が低く、十分ではない。 From the results in Tables 1 to 7, the binder resin (A), the compound (B) having an acidic group, the organic solvent (C), and one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom And a compound (D) having a hydrocarbyloxy group or a hydroxy group bonded to the atom, and the compound (B) having an acidic group is composed of an aliphatic compound, an aromatic compound, and a heterocyclic compound. Resin of Examples 1 to 46, which is at least one selected from the group and has a total content of compound (B) and compound (D) in the range of 10 to 50 with respect to 100 parts by weight of binder resin (A) When a resin film is formed on a substrate using the composition, the adhesion of the obtained resin film to the substrate is high.
On the other hand, in the case of Comparative Examples 1 and 2 in which the total content of the compound (B) and the compound (D) is outside the range defined by the present invention, or the compound (B) and the compound (D defined by the present invention) In the case of Comparative Examples 3 and 4 in which only one of them is used, or in Comparative Example 5 in which neither Compound (B) nor Compound (D) is used, Adhesion is low and not sufficient.

Claims (19)

  1. 　バインダー樹脂（Ａ）、酸性基を有する化合物（Ｂ）、有機溶媒（Ｃ）、並びにケイ素原子、チタン原子、アルミニウム原子、及びジルコニウム原子の中から選ばれる１つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物（Ｄ）を含有してなり、
    　前記酸性基を有する化合物（Ｂ）が、脂肪族化合物、芳香族化合物、及び複素環化合物からなる群より選ばれた少なくとも１種であり、
    　前記化合物（Ｂ）と前記化合物（Ｄ）の合計含有量が前記バインダー樹脂（Ａ）１００重量部に対して１０～５０重量部であることを特徴とする樹脂組成物。     Binder resin (A), acidic group-containing compound (B), organic solvent (C), and one atom selected from silicon atom, titanium atom, aluminum atom, and zirconium atom, and bonded to the atom A compound (D) having a hydrocarbyloxy group or a hydroxy group,
    The acidic group-containing compound (B) is at least one selected from the group consisting of aliphatic compounds, aromatic compounds, and heterocyclic compounds,
    A resin composition, wherein the total content of the compound (B) and the compound (D) is 10 to 50 parts by weight with respect to 100 parts by weight of the binder resin (A).
  2. 　感放射線化合物（Ｅ）をさらに含有してなる請求項１に記載の樹脂組成物。 The resin composition according to claim 1, further comprising a radiation-sensitive compound (E).
  3. 　前記酸性基を有する化合物（Ｂ）の酸性基が、カルボキシ基、チオール基、またはカルボキシメチレンチオ基である請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the acidic group of the compound (B) having an acidic group is a carboxy group, a thiol group, or a carboxymethylenethio group.
  4. 　前記酸性基を有する化合物（Ｂ）の、酸性基の酸解離定数ｐＫａ（酸性基が２つ以上ある場合は第一酸解離定数ｐＫａ１）が３．５以上５．０以下の範囲にある請求項１～３のいずれか１項に記載の樹脂組成物。 The acid dissociation constant pKa of the acidic group-containing compound (B) (if there are two or more acidic groups, the first acid dissociation constant pKa1) is in the range of 3.5 to 5.0. 4. The resin composition according to any one of 1 to 3.
  5. 　前記酸性基を有する化合物（Ｂ）は、酸性基を２つ以上含有する請求項１～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the compound (B) having an acidic group contains two or more acidic groups.
  6. 　架橋剤（Ｆ）をさらに含有してなる、請求項１～５のいずれか１項に記載の感放射線樹脂組成物。 The radiation-sensitive resin composition according to any one of claims 1 to 5, further comprising a crosslinking agent (F).
  7. 　前記架橋剤（Ｆ）が、エポキシ化合物である、請求項６に記載の感放射線樹脂組成物。 The radiation-sensitive resin composition according to claim 6, wherein the crosslinking agent (F) is an epoxy compound.
  8. 　前記エポキシ化合物が、脂環構造を有するエポキシ化合物である、請求項７に記載の樹脂組成物。 The resin composition according to claim 7, wherein the epoxy compound is an epoxy compound having an alicyclic structure.
  9. 　前記バインダー樹脂（Ａ）が、プロトン性極性基を有する環状オレフィン重合体、アクリル樹脂、カルド樹脂、ポリシロキサン、及びポリイミドから選ばれる１種以上の重合体である、請求項１～８のいずれか１項に記載の樹脂組成物。 The binder resin (A) is one or more polymers selected from cyclic olefin polymers having a protic polar group, acrylic resins, cardo resins, polysiloxanes, and polyimides. 2. The resin composition according to item 1.
  10. 　前記化合物（Ｄ）が、更にプロトン性極性基と反応し得る官能基を有する化合物である請求項１～９のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 9, wherein the compound (D) is a compound further having a functional group capable of reacting with a protic polar group.
  11. 　前記化合物（Ｄ）のプロトン性極性基と反応し得る官能基が、イソシアネート基、メルカプト基、エポキシ基、又はアミノ基である請求項１０に記載の樹脂組成物。 The resin composition according to claim 10, wherein the functional group capable of reacting with the protic polar group of the compound (D) is an isocyanate group, a mercapto group, an epoxy group, or an amino group.
  12. 　前記化合物（Ｂ）の含有量が、前記化合物（Ｄ）の含有量以上である請求項１～１１のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 11, wherein the content of the compound (B) is not less than the content of the compound (D).
  13. 　請求項１～１２のいずれか１項に記載の樹脂組成物を用いて、樹脂膜を基板上に形成する工程を有する積層体の製造方法。 A method for producing a laminate comprising a step of forming a resin film on a substrate using the resin composition according to any one of claims 1 to 12.
  14. 　前記基板上に形成された樹脂膜に活性放射線を照射して前記樹脂膜に潜像パターンを形成する工程、及び前記樹脂膜に現像液を接触させることにより潜像パターンを顕在化させて、前記樹脂膜をパターン化する工程をさらに有する、請求項１３に記載の積層体の製造方法。 Irradiating actinic radiation to the resin film formed on the substrate to form a latent image pattern on the resin film, and exposing the latent image pattern by bringing a developer into contact with the resin film, The manufacturing method of the laminated body of Claim 13 which further has the process of patterning a resin film.
  15. 　前記基板上に形成されたパターン化樹脂膜を加熱してパターン形状を変形させる工程をさらに有する請求項１４に記載の積層体の製造方法。 The method for manufacturing a laminate according to claim 14, further comprising a step of deforming a pattern shape by heating the patterned resin film formed on the substrate.
  16. 　前記基板上に形成された樹脂膜を架橋する工程をさらに有する請求項１３～１５のいずれか１項に記載の積層体の製造方法。 The method for producing a laminate according to any one of claims 13 to 15, further comprising a step of crosslinking a resin film formed on the substrate.
  17. 　請求項１～１２のいずれか１項に記載の樹脂組成物からなる樹脂膜を基板上に積層してなる積層体。 A laminate obtained by laminating a resin film made of the resin composition according to any one of claims 1 to 12 on a substrate.
  18. 　前記樹脂膜がパターン化樹脂膜である請求項１７に記載の積層体。 The laminate according to claim 17, wherein the resin film is a patterned resin film.
  19. 　請求項１７又は１８に記載の積層体からなる半導体デバイス。 A semiconductor device comprising the laminate according to claim 17 or 18.
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