Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
• • 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
  • C08G59/20—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 epoxy compounds used
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
  • C08L101/08—Carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to a resin composition and a resin film, and more particularly to a resin composition and a resin film containing a carboxyl group-containing resin.
• Various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and electronic parts such as color filters and black matrices are protective films for preventing deterioration or damage, element surfaces
• Various resin films are provided as a planarizing film for planarizing the surface of a substrate having a wiring, an electrical insulating film for maintaining electrical insulation, and the like.
• a resin film as a pixel separation film is provided in order to separate the light emitting body portion.
• a resin film as an interlayer insulating film is provided in order to insulate between the wirings arranged in layers.
• Patent Document 1 proposes a negative photosensitive resin composition comprising a cyclic olefin polymer having a protic polar group, an unsaturated group-containing compound, and a radical generating photopolymerization initiator. According to this resin composition, it is possible to form a resin film which is excellent in pattern formability by development, transparency, and heat resistance, and in which generation of outgas is suppressed.
• materials such as glass have been generally used as a substrate of a display element.
• the resin film is cured at a high curing temperature of, for example, 200 ° C. or more to accelerate the curing reaction and make the resin film rich in chemical resistance. It was possible to form.
• a flexible plastic film or the like as a substrate instead of a glass substrate.
• the heat resistance of the plastic substrate is lower than the heat resistance of the glass substrate. Therefore, in order to form a resin film on a plastic substrate, it is necessary to lower the curing temperature when curing the resin film. Therefore, development of a resin composition capable of forming a resin film having high chemical resistance even under low temperature curing conditions is required.
• the present invention provides a resin composition which is compatible with securing the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film.
• the purpose is Another object of the present invention is to provide a resin film having excellent chemical resistance.
• the present inventors diligently studied for the purpose of solving the above-mentioned problems. Then, when the present inventors coexist a resin having a predetermined functional group, a polyfunctional vinyl ether compound, and a predetermined nitrogen-containing condensed heterocyclic compound in the resin composition, the resin composition itself is preserved. The inventors have newly found that compatibility between securing stability and enhancing the chemical resistance of a resin film obtained using such a resin composition has been newly found, and the present invention has been completed.
• the object of the present invention is to advantageously solve the above-mentioned problems, and the resin composition of the present invention comprises a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing nitrogen-containing resin having 3 atoms. And a fused heterocyclic compound.
• the nitrogen-containing fused heterocyclic compound is preferably a benzotriazole-based compound. If the resin composition contains a benzotriazole-based compound, it is possible to achieve both better preservation of the storage stability of the resin composition itself and enhancement of the chemical resistance of the obtained resin film. .
• the resin composition of this invention further contains a polyfunctional epoxy compound. If the resin composition further contains a polyfunctional epoxy compound, the crack resistance of the resulting resin film can be further improved.
• the said polyfunctional epoxy compound has an alicyclic epoxy group. If the polyfunctional epoxy compound contained in the resin composition has an alicyclic epoxy group, the crack resistance of the obtained resin film can be further improved.
• the carboxyl group-containing resin is a resin containing a cyclic olefin monomer unit. If the resin composition is a resin containing cyclic olefin monomer units, the amount of outgassing from the obtained resin film can be suppressed, and the water absorbency of the obtained resin film can be reduced.
• the resin composition of this invention contains the said nitrogen-containing fused heterocyclic compound in the ratio of 1 mass part or more with respect to 100 mass parts of said carboxyl group-containing resin. If the content ratio of the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is not less than the above lower limit value, the crack resistance of the obtained resin film can be further improved.
• the present invention has an object to advantageously solve the above-mentioned problems, and the resin film of the present invention is characterized by being formed using any of the above-mentioned resin compositions. Since the resin film of the present invention is formed using the resin composition of the present invention, it is excellent in chemical resistance.
• the present invention it is possible to provide a resin composition which is compatible with securing the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film. Further, according to the present invention, a resin film having excellent chemical resistance can be provided.
• the resin composition of the present invention can be suitably applied to various elements, parts, and the like to form a resin film that can function as a protective film, a planarization film, an insulating film, and the like.
• the resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms. Securing the storage stability of the resin composition itself by blending a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms in the resin composition; It can be compatible with improving the chemical resistance of the resin film obtained by using such a resin composition.
• the reactivity between the carboxyl group contained in the carboxyl group-containing resin and the polyfunctional vinyl ether compound is good, and the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms exhibits appropriate basicity.
• the carboxyl group contained in the resin and the polyfunctional vinyl ether compound can start the reaction at a low temperature, and the nitrogen-containing fused heterocyclic compound which is basic promotes such reaction. It is thought that acting as it works. From these reasons, it is presumed that according to the resin composition of the present invention, a resin film having good chemical resistance can be formed. Furthermore, the resin composition of the present invention preferably further comprises a polyfunctional epoxy compound.
• each component contained in a resin composition is demonstrated.
• the carboxyl group-containing resin is not particularly limited as long as it is constituted by a polymer having a carboxyl group, and any resin can be used.
• Examples of such carboxyl group-containing resin include (co) polymers containing a carboxyl group-containing monomer unit (hereinafter also referred to as "carboxyl group-containing monomer unit").
• (co) polymer means a polymer or a copolymer.
• the (co) polymer containing a carboxyl group-containing monomer unit is formed, for example, using an ethylenically unsaturated carboxylic acid monomer and a derivative thereof, and a carboxyl group-containing cyclic olefin monomer and a derivative thereof ( Co) polymers are mentioned.
• Ethylenically unsaturated carboxylic acid monomers include ethylenically unsaturated monocarboxylic acids and their derivatives, ethylenically unsaturated dicarboxylic acids and their acid anhydrides and their derivatives.
• Examples of ethylenically unsaturated monocarboxylic acids include (meth) acrylic acid and crotonic acid.
• (meth) acrylic acid means acrylic acid or methacrylic acid.
• examples of the derivative of the ethylenically unsaturated monocarboxylic acid include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate and the like.
• examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid and itaconic acid.
• cyclic olefin monomer for example, 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2 -Ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 4-hydroxycarbonyl Tetracyclo [6.2.1.1 3, 6 . 0 2,7 ] dodec-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and the like.
• the (co) polymer containing a carboxyl group-containing monomer unit may be a polymer composed of one of the above monomers, or the above monomers and these monomers And copolymers with other monomers copolymerizable therewith.
• an N-substituted imide group which can be represented by the following formula (A) as disclosed in JP-A-2015-25892 Cyclic olefin monomer, cyclic olefin monomer having an oxygen-containing group such as ester group or acid anhydride group, cyclic olefin monomer having a nitrogen-containing group such as cyano group, cyclic olefin monomer having a sulfonyl group And cyclic olefin monomers having a silyl group or cyclic olefin monomers having a halogen atom.
• A N-substituted imide group which can be represented by the following formula (A) as disclosed in JP-A-2015-25892 Cyclic olefin monomer, cyclic olefin monomer having an oxygen-containing group such as ester group or acid anhydride group, cyclic olefin monomer having a nitrogen-containing group such as cyano group
• X represents a hydrogen atom or a linear, cyclic or branched alkyl group having 1 to 16 carbon atoms, or an aryl group such as a benzyl group, and n is 1 or 2.
• the proportion of the carboxyl group-containing monomer unit is 10 mass, based on 100% by mass of all monomer units constituting the (co) polymer. % Or more, preferably 15% by mass or more, and may be 100% by mass.
• the proportion of the carboxyl group-containing monomer unit in the (co) polymer can be measured by 1 H-NMR or the like.
• the (co) polymer containing a carboxyl group-containing monomer unit is, for example, an acrylic resin constituted by a polymer obtained using the above-mentioned acrylic acid ester monomer; And polyamide resins, polyester resins, polyurethane resins, polyolefin resins, and polymers composed of (co) polymers that can be obtained using the above-mentioned carboxyl group-containing monomer and any other monomer. It may be cycloolefin resin, and polysiloxane resin.
• a polycycloolefin resin is preferable as the carboxyl group-containing resin because the amount of outgas can be suppressed and the water absorption is low.
• the polycycloolefin resin is a resin containing cyclic olefin monomer units.
• the cyclic olefin monomer unit includes the carboxyl group-containing cyclic olefin monomer unit as described above and the other cyclic olefin monomer units.
• polycycloolefin resin which is a carboxyl group-containing resin
• a resin containing a carboxyl group-containing cyclic olefin monomer unit is more preferable, and a carboxyl group-containing cyclic olefin monomer unit and the above-mentioned formula (A)
• resins comprising cyclic olefin monomer units having the N-substituted imide group which is represented.
• 4-hydroxycarbonyltetracyclo [6.2.1.13 , 6 .
• TCDC dodeca-9-ene
• NBPI carboximide
• the content ratio of cyclic olefin monomer units in the resin containing cyclic olefin monomer units constitutes the resin
• the total monomer unit content is preferably 100% by mass, more preferably 50% by mass, more preferably 70% by mass, still more preferably 90% by mass, and 100% by mass of cyclic olefins It may be a monomer unit.
• the content ratio of the carboxyl group-containing cyclic olefin monomer unit is the total unit amount constituting the resin It is preferable that it is 100 mass%, and it is more than 40 mass%, It is more preferable that it is 55 mass%, and less than 100 mass% is preferable.
• the proportion of each monomer unit in the resin containing cyclic olefin monomer units can be measured by 1 H-NMR.
• the (co) polymer containing a carboxyl group-containing monomer unit a commercially available product or a (co) polymer produced according to a known production method can be used.
• the production method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
• polymerization mode addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization and ring-opening polymerization can be adopted.
• a polymerization initiator a known polymerization initiator can be used as a polymerization initiator.
• various cyclic olefin monomers are polymerized according to a method using a known ring-opening polymerization catalyst and additives as described in, for example, JP-A-2015-25892 (co )
• the (co) polymer may be hydrogenated in the presence of a known hydrogenation catalyst.
• a vinyl ether compound having a functional group number of 2 or more can be used as a polyfunctional vinyl ether compound.
• the number of functional groups of the polyfunctional vinyl ether compound, that is, the number of vinyl ether structures contained in one molecule is preferably 2 or more, and more preferably 2 or more and 5 or less.
• vinyl ether compound having 2 functional groups examples include 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol Divinyl ether and cyclohexanediol divinyl ether can be mentioned. Among them, 1,4-butanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and cyclohexanediol divinyl ether are preferable. Moreover, as a vinyl ether compound having a functional group number of 3, trimethylolpropane trivinyl ether and trimethylolpropane ethoxylate trivinyl ether are preferable.
• the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is a compound containing 3 nitrogen atoms in the constituent atoms of the fused heterocycle.
• the “nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms” is not particularly limited as long as the constituent atoms of one fused heterocycle contain 3 nitrogen atoms, and may include any compound. More specifically, the “nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms” may contain two or more fused heterocyclic rings containing three nitrogen atoms in the constituent atoms in one compound.
• the nitrogen atom may be contained in a structure other than the nitrogen-containing fused heterocyclic structure constituting the compound.
• Examples of the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms include a compound that can be represented by the following general formula (1), and a compound that has a structure that can be represented by the following general formula (1).
• any three of G 1 to G 9 are nitrogen atoms, the others are carbon atoms, R 1 is a hydrogen atom or an organic group, R 2 is a hydrogen atom, halogen It is a group, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms.
• the organic group which may be R 1 contained in the formula (1) is a phenol group which may have one or more substituents, and carbon which may have one or more substituents. It may be a linear or branched alkyl group of 1 to 10.
• a substituent of the phenol group which may have one or more substituents an alkyl group having 1 to 10 carbon atoms, 3,4,5,6-tetrahydro-N-methylphthalimide group, And 1-methyl-1-phenylethyl group.
• substituent of the linear or branched alkyl group having 1 to 10 carbon atoms which may have one or more substituents include a hydroxyl group and the like.
• the compound which may be a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms may be a compound having the structures [1] and [1] ′ which can be represented by the above formula (1). Specifically, such a compound has two structures [1] and [1] ′ (wherein structures [1] and [1] ′ are both particularly limited as long as they can be represented by the above formula (1)). And C 1 to C 10 alkylene group (—C m H 2 m ⁇ ; where m is an integer of 1 to 10); formed by interconnected by), the general formula (2): [1] -C m H 2m - may be a compound that may be represented by [1] '.
• the alkylene group having 1 to 10 carbon atoms, which is a linking group is bonded to each R 1 contained in the structures [1] and [1] ′.
• benzotriazoles in which G 1 to G 3 are nitrogen atoms and G 4 to G 9 are carbon atoms in the above formulas (1) and (2) Preferred are compounds. If the resin composition contains a benzotriazole-based compound, it is possible to more effectively ensure the storage stability of the resin composition itself and to enhance the chemical resistance of the obtained resin film. it can.
• benzotriazole compounds satisfying the above formula (1) include 1H-benzotriazole-1-methanol, 1,2,3-benzotriazole (manufactured by Johoku Chemical Co., Ltd., “BT-120”), 2- (2) '-Hydroxy-5'-methylphenyl) benzotriazole (manufactured by Johoku Chemical, "JF-77”), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro Benzotriazole (manufactured by Johoku Chemical, "JF-79”), 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole (manufactured by Johoku Chemical, "JF-80”) , 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole (manufactured by Johoku Chemical, “JF-83”), 2- [2-hydroxy-3- (3-
• the content of the nitrogen-containing fused heterocyclic compound in the resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 100 parts by mass of the carboxyl group-containing resin. It is less than 20 parts by mass, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 7 parts by mass or less. If the content ratio of the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is not less than the above lower limit value, the crack resistance of the obtained resin film can be further improved.
• the resin film can be favorably formed by suppressing the viscosity of the resin composition from excessively increasing. it can.
• the polyfunctional epoxy compound is not particularly limited, and includes compounds having two or more epoxy groups in one molecule.
• the crack resistance of the obtained resin film can be further improved. It is presumed that this is because the polyfunctional epoxy compound present in the resin composition can appropriately suppress an increase in internal stress due to the carboxylic acid and the polyfunctional vinyl ether in the resin film.
• Examples of compounds having two or more epoxy groups in one molecule include epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone, tris (2,3-epoxypropyl) isocyanurate, 1,4- Butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-tris [p- (2,3-Epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′-methylene bis (N, N-diglycidyl aniline), 3,4-epoxycyclohexylmethyl-3,4 -Epoki
• EPOID GT-401 EPOID GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009.
• the polyfunctional epoxy compound preferably has an alicyclic epoxy group.
• the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and usually 6 or less. It is.
• epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone (the number of alicyclic epoxy groups: 4) is preferable.
• the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound is a unit structure (one molecule) per unit structure (one molecule) when the polyfunctional epoxy compound is a polymer composed of a repeating structural unit containing an alicyclic epoxy group. Means the number of alicyclic epoxy groups.
• the resin composition of the present invention may contain optional components such as a silane coupling agent, an antioxidant, and a surfactant.
• optional components known ones can be used (see, for example, WO 2015/033901 and JP-A-2015-25892). And content of these additives can also be suitably adjusted within a general range, unless the effect of the present invention is spoiled.
• solvents that may be contained in the resin composition of the present invention known organic solvents used for preparation of the resin composition can be used (see, for example, WO 2015/033901). Among them, solvents containing diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether can be suitably used.
• the method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition may be mixed by a known method.
• the method of mixing is not particularly limited, and it is possible to obtain a solution or dispersion in which each component is dissolved or dispersed in a solvent by adding and mixing each component constituting the resin composition to the solvent. it can.
• a mixing method using stirring using a stirrer, a high speed homogenizer, a disper, a planetary stirrer, a twin screw stirrer, a ball mill, a triple roll, etc. may be mentioned.
• the solution or dispersion obtained by mixing may be filtered using, for example, a filter having a pore diameter of about 0.45 ⁇ m.
• the resin film of the present invention is characterized by being formed using the resin composition of the present invention. Since the resin film of the present invention is formed using the resin composition of the present invention, it is excellent in chemical resistance.
• the resin film of the present invention can be formed by applying the resin composition of the present invention on a desired substrate. That is, the resin film of the present invention is a dried product of the above-described resin composition of the present invention, and generally, at least a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms. Contains Furthermore, it is preferable that the resin film of this invention contains a polyfunctional epoxy compound.
• the suitable abundance ratio of those each component is with the suitable abundance ratio of each component in a resin composition. It is the same.
• the polyfunctional vinyl ether compound contained in the resin film, the polyfunctional epoxy compound which may optionally be contained, etc. may be crosslinked at the time of the crosslinking treatment which can be optionally carried out.
• the resin film may contain the cross-linked product of the above-mentioned polyfunctional vinyl ether compound and polyfunctional epoxy compound.
• the substrate for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate or the like can be used. Further, a substrate obtained by forming a thin transistor type liquid crystal display element, a color filter, a black matrix or the like on a glass substrate or a plastic substrate used in the display field is also suitably used. Among them, since the resin composition of the present invention can be cured at a low temperature, the resin film of the present invention formed using such a resin composition can be suitably provided on a plastic substrate.
• the application method is, for example, a method of removing the solvent after applying the resin composition on a substrate such as a plastic substrate.
• a method of applying the resin composition for example, 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 are employed. be able to.
• the solvent can be removed, for example, by drying.
• the drying conditions vary depending on the type of each component, the blending ratio, the heat resistance temperature of the substrate such as a plastic substrate, etc., but usually the temperature conditions of 30 ° C. to 150 ° C., preferably 60 ° C.
• the resin composition of the present invention can be 0.5 minutes to 90 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 30 minutes. According to the resin composition of the present invention, a resin film having excellent chemical resistance can be obtained even when the temperature at the time of drying is equal to or lower than the upper limit. Moreover, if the temperature at the time of drying is made more than the above-mentioned lower limit, the chemical resistance of the resin film can be sufficiently improved.
• the solvent is removed to obtain a resin film, and the obtained resin film is laminated on a substrate to obtain a substrate having a resin film. It is a method to form.
• the solvent can be removed, for example, by drying. Drying conditions can be suitably selected according to the kind and compounding ratio of each component. Drying conditions can be usually set to temperature conditions of 30 ° C. or more and 150 ° C. or less for 0.5 minutes or more and 90 minutes or less.
• a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like can be used.
• the thickness of a resin film is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.5 ⁇ m to 50 ⁇ m, still more preferably 0.5 ⁇ m to 30 ⁇ m, and particularly preferably 0.5 ⁇ m to 10 ⁇ m.
• the resin composition of the present invention even when the thickness of the resin film is relatively thin, chemical resistance can be sufficiently improved.
• a crosslinking process can be performed about the resin film formed of the above-mentioned application method or film lamination method as needed.
• the crosslinking treatment is not particularly limited, and can be performed by a general method as disclosed in, for example, JP-A-2015-25892.
• the resin film of the present invention preferably has a light transmittance of 95% or more at a wavelength of 400 nm when measured without passing through the bleaching exposure step.
• the light transmittance can be measured, for example, according to the method described in the examples.
• the resin film of the present invention can achieve the high light transmittance as described above without performing a so-called bleaching exposure step.
• a bleaching exposure process means the operation for exposing this resin film to overexposure conditions, and fading a colored resin film.
• the resin film formed under a given condition is 100 J in terms of the exposure dose of g-line (wavelength 436 nm), h-line (wavelength 405 nm), or i-line (wavelength 365 nm) It means a process of exposing to light of a light amount in the range of from / m 2 to 20,000 J / m 2 .
• ⁇ Storage stability of resin composition The viscosities of the resin compositions prepared in Examples and Comparative Examples were measured with an E-type viscometer according to "10 Viscosity Method with a Conical Plate-Type Rotational Viscometer" described in JIS Z 8803: 2011. The viscosity of the resin composition immediately after preparation was V0. In addition, the resin composition was sealed in a light shielding bottle, and the viscosity V1 of the resin composition after stored for 1 week in a clean room (temperature 23 ° C., humidity 45%) was measured in the same manner. Then, the viscosity change rate (%) was calculated according to the formula:
• ⁇ Chemical resistance of resin film> The resin composition prepared in Examples and Comparative Examples is applied onto a silicon wafer substrate by spin coating, and heat dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to pre-bake a film thickness of 2.0 ⁇ m. A finished resin film was formed. Next, the resin film was subjected to post-baking in an air atmosphere at 130 ° C. for 20 minutes using an oven to obtain a laminate of a silicon wafer substrate having a post-baked resin film on the surface. The laminated body obtained as described above is used as a test body, and is immersed in 200 ml of chemical for 5 minutes, and the ratio of the film thickness after immersion when the film thickness before immersion is 100% (%) Was calculated.
• a Cu thin film with a film thickness of 100 nm was formed on a glass substrate (Corning Inc., product name: Corning 1737) using a sputtering apparatus.
• the Cu thin film was patterned using a photoresist to prepare a comb electrode substrate having a Cu wiring width of 7 ⁇ m and a wiring distance of 7 ⁇ m.
• the resin compositions prepared in Examples and Comparative Examples are applied by spin coating onto the comb electrode substrate, and heat dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to give a film thickness of 2.0 ⁇ m.
• a resin film was formed.
• the resin film is subjected to post-baking heating at 130 ° C.
• the resin composition obtained in the example is applied on a glass substrate (Corning Inc., product name Corning 1737) by a spin coating method, and dried by heating (prebaking) at 90 ° C. for 2 minutes using a hot plate. A resin film of 2.0 ⁇ m was formed. Then, using an oven, post-baking was performed by heating at 130 ° C. for 20 minutes in an air atmosphere to obtain a laminate of the resin film and the glass substrate. The obtained laminate was measured at a wavelength of 400 nm to 800 nm using a spectrophotometer V-560 (manufactured by JASCO Corporation). The light transmittance (%) at 400 nm was calculated from the measurement results. In addition, the light transmittance (%) of the resin film was computed by the conversion value in case the thickness of a resin film is 2.0 micrometers by using as a blank the glass substrate to which the resin film is not attached.
• Example 1 Preparation of Carboxyl Group-Containing Resin> 31.5 mol% of N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI), which is a cyclic olefin monomer having an N-substituted imide group, and carboxyl 4-hydroxy carbonyl tetracyclo [6.2.1.1 3, 6 .
• NBPI N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide
• the obtained polymerization reaction solution is put into an autoclave, and the hydrogenation reaction is carried out by stirring for 5 hours under the conditions of 150 ° C. and hydrogen pressure 4 MPa, and a carboxyl group-containing compound composed of an alicyclic olefin copolymer A solution containing a polyolefin resin was obtained.
• the polymerization conversion ratio of the above-mentioned alicyclic olefin copolymer is 99.9%
• the polystyrene conversion weight average molecular weight is 5,280
• the number average molecular weight is 3,490
• the molecular weight distribution is 1.51
• the hydrogenation ratio is 99.9 %Met.
• solid content concentration of the solution containing carboxyl group-containing polyolefin resin was 32.0 mass%.
• ⁇ Preparation of Resin Composition 100 parts of the carboxyl group-containing polyolefin resin obtained above, 40 parts of 1,4-cyclohexanedimethanol divinyl ether as a polyfunctional vinyl ether compound (manufactured by Nippon Carbide Co., Ltd., “CHDVE”), epoxidation as a polyfunctional epoxy compound Butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Epolide GT 401) 40 parts, nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms 1H-as a benzotriazole based compound 5 parts of benzotriazole-1-methanol (made by Tokyo Chemical Industry Co., Ltd.), 2 parts of glycidoxypropyltrimethoxysilane (made by XIAMETER: OFS 6040) as a silane coupling agent, pent
• Example 2 A resin composition was prepared in the same manner as in Example 1 except that the compounding amount of the benzotriazole compound was changed to 5 parts, and various evaluations and the like were performed. The results are shown in Table 1.
• Example 3 1,4-butanediol divinyl ether (BDVE) was used as the polyfunctional vinyl ether compound.
• DEGDVE diethylene glycol divinyl ether
• Example 5 trimethylolpropane ethoxylate trivinyl ether was used as the polyfunctional vinyl ether compound.
• Example 6 trimethylolpropane trivinyl ether was used as the polyfunctional vinyl ether compound.
• cyclohexanediol divinyl ether (CHODVE) was used as the polyfunctional vinyl ether compound.
• a resin composition was prepared in the same manner as in Example 2 except for these points, and various evaluations and the like were performed. The results are shown in Table 1.
• Example 8 A resin composition was prepared in the same manner as in Example 2 except that the polyfunctional epoxy compound was not blended, and various evaluations and the like were performed. The results are shown in Table 1.
• Example 8 A resin composition was prepared in the same manner as in Example 2 except that monofunctional monovinyl ether compounds shown in Table 1 were respectively blended in place of the polyfunctional vinyl ether compound, and various evaluations and the like were performed. The results are shown in Table 1. In these examples, the chemical resistance of the obtained resin film was low, and cracks were generated by immersion in acetone, so that the insulation reliability was not evaluated.
• GT401 is an epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone (manufactured by Daicel Chemical Industries, Ltd .
• TPA520 is a compound of 4,4 ′-[1- [4- [1-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro-5-oxo Ester (2.0 molar) with 2-naphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid chloride),
• OFFS6040 is glycidoxypropyltrimethoxysilane (manufactured by XIAMETER: OFS6040),
• Irg1010 is pentaerythritol-tetrakis [3- (3,5-di
• Comparative Examples 1 to 7 in which the benzotriazole-based compound which is a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is not blended, securing the storage stability of the resin composition itself, and the obtained resin film It can be seen that it was not compatible with the improvement of the chemical resistance of Among them, in Comparative Example 5 in which homophthalic acid was blended instead of the nitrogen-containing fused heterocyclic compound, the storage stability of the resin composition was lowered, and the insulation reliability of the resin film was not obtained. This is because the crosslinking reaction occurs between the polyfunctional vinyl ether compound and the polyfunctional epoxy compound contained in the resin composition, the viscosity increases, the storage stability decreases, and the resin film is further contained.
• the present invention it is possible to provide a resin composition which is compatible with securing the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film. Further, according to the present invention, a resin film having excellent chemical resistance can be provided.

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