Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • 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.

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