WO2010110323A1 - 重合体、水素添加物、樹脂組成物、樹脂膜及び電子部品 - Google Patents
重合体、水素添加物、樹脂組成物、樹脂膜及び電子部品 Download PDFInfo
- Publication number
- WO2010110323A1 WO2010110323A1 PCT/JP2010/055095 JP2010055095W WO2010110323A1 WO 2010110323 A1 WO2010110323 A1 WO 2010110323A1 JP 2010055095 W JP2010055095 W JP 2010055095W WO 2010110323 A1 WO2010110323 A1 WO 2010110323A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- acid
- ene
- resin composition
- group
- Prior art date
Links
- 0 *N(C(C1C2C3C=CC1C3)=O)C2=O Chemical compound *N(C(C1C2C3C=CC1C3)=O)C2=O 0.000 description 1
Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- 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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F32/04—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
- C08G2261/724—Hydrogenation
Definitions
- the present invention relates to a polymer, a hydrogenated product of the polymer, a resin composition containing the polymer and / or the hydrogenated product, a resin film formed from the resin composition, and an electronic component having the resin film About. More specifically, the present invention relates to a polymer having high solubility in a polar solvent, low water absorption, and high adhesion to a substrate, a hydrogenated product of the polymer, the polymer and / or the hydrogenated product. The present invention relates to a resin composition using a resin, a resin film formed from the resin composition, and an electronic component having the resin film.
- polymers of cyclic olefins having functional groups and hydrogenated products thereof have attracted attention as functional group-containing polymers having excellent heat resistance, electrical properties, low water absorption, and the like.
- This polymer also has excellent adhesion to inorganic materials such as metals and glass, and is also compatible with organic materials such as antioxidants, plasticizers, UV absorbers, colorants, curing agents, and flame retardants. Due to its superiority, it is expected to be used for a wide range of composite materials.
- Patent Document 1 discloses a ring-opening polymer of a cyclic olefin having an N-substituted cyclic imide structure as a spiro ring and a hydrogenated product thereof. It has been disclosed that this polymer and its hydrogenated product are excellent in heat resistance and electrical characteristics.
- Patent Document 2 discloses an addition polymer, ring-opening polymer and hydrogenated product of an N-substituted cyclic imide structure-containing cyclic olefin having a carboxylic acid ester in the substituent. It is disclosed that this polymer and its hydrogenated product are excellent in heat resistance, solubility in polar solvents, and adhesion to inorganic substrates.
- Patent Document 3 discloses a ring-opening polymer of a cyclic olefin having a cyclic imide structure containing an N-alkyl group, N-cycloalkyl group or N-aryl group, and a hydrogenated product thereof. This polymer and its hydrogenated product are disclosed to exhibit high thermal oxidation stability.
- the polymers specifically disclosed in Patent Documents 1 to 3 and hydrogenated products thereof are propylene glycol monomethyl ether acetate (PGMEA), which is widely used particularly in resin compositions containing a crosslinking agent and a radiation-sensitive compound.
- PGMEA propylene glycol monomethyl ether acetate
- MIBK methyl isobutyl ketone
- other various solvents such as MIBK used as a cleaning solvent for resin compositions are not soluble in highly volatile polar solvents. It was limited. Further, depending on the application, further improvements in water absorption and adhesion characteristics have been demanded.
- the present invention provides a polymer of a cyclic olefin excellent in low water absorption, solubility in a polar solvent, and adhesion to a substrate, and a hydrogenated product thereof.
- the present inventors have polymerized a structure in which a cyclic imide skeleton having a substituent having a specific structure on a nitrogen atom and a cyclic olefin share one carbon-carbon bond. It has been found that a polymer of a cyclic olefin in a unit and a hydrogenated product thereof are excellent in low water absorption, solubility in a polar solvent and adhesion to a substrate, and the present invention has been completed based on these findings. .
- a polymer comprising polymerized units of the monomer represented by the general formula (1).
- R 1 represents a branched alkyl group having 5 to 16 carbon atoms.
- the polymer is preferably a polymer having a polymerization unit copolymerizable therewith in addition to the polymerization unit of the monomer represented by the general formula (1).
- the copolymerizable monomer is preferably a cyclic olefin monomer having a protic polar group, and more preferably a carboxyl group-containing cyclic olefin monomer. .
- the polymer is preferably a ring-opening polymer.
- a hydrogenated product of the ring-opening polymer is provided.
- the resin composition containing the polymer which contains the polymerization unit of the monomer represented by General formula (1), and / or its hydrogenated product (A), and a solvent (B). is provided.
- a polymer comprising polymerized units of the monomer represented by the general formula (1) and / or its hydrogenated product (A), solvent (B) and crosslinking agent (C) A resin composition containing is provided.
- the polymer and / or its hydrogenated substance (A), solvent (B), and radiation sensitive compound (D) which contain the polymerization unit of the monomer represented by General formula (1) ) Is provided.
- the polymer comprising the polymerized units of the monomer represented by the general formula (1) and / or its hydrogenated product (A), solvent (B), and crosslinking agent (C)
- a resin composition containing the radiation-sensitive compound (D) is also provided.
- an electronic component having the resin film is provided.
- a polymer having excellent solubility in a polar solvent, low water absorption and high adhesion, a hydrogenated product of the polymer, a resin composition having the polymer and / or the hydrogenated product A resin film formed from the resin composition and an electronic component having the resin film can be obtained.
- the polymer and hydrogenated product of the present invention are highly reliable and excellent in various electrical characteristics (for example, low dielectric constant characteristics, low leakage current characteristics, high breakdown voltage characteristics)
- it since it has high transparency and is excellent in pattern formation by development, it can be suitably used as a resin used for resists, electrical insulating films for semiconductor production, transparent films for display elements, and the like.
- the polymer of the present invention is a polymer comprising a polymer unit of a monomer represented by the following general formula (1).
- R 1 represents a branched alkyl group having 5 to 16 carbon atoms.
- R 1 represents a branched alkyl group having 5 to 16 carbon atoms.
- Examples of the branched alkyl group having 5 to 16 carbon atoms include 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methyl Examples include heptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group and the like.
- a branched alkyl group having 6 to 14 carbon atoms is preferable and a branched alkyl group having 7 to 10 carbon atoms is more preferable because of excellent heat resistance and solubility in a polar solvent.
- the carbon number is 4 or less, the solubility in a polar solvent is poor, when the carbon number is 17 or more, the heat resistance is poor, and the patterned resin film is melted by heat and the pattern disappears. There is.
- the monomer represented by the general formula (1) can be easily produced. That is, the monomer represented by the general formula (1) can be obtained by an amidation reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride.
- the target monomer represented by the general formula (1) can be efficiently isolated by separating and purifying the reaction solution of the amidation reaction by a known method.
- the polymer of the present invention is a polymer comprising polymerized units of the monomer represented by the general formula (1).
- the polymer of the present invention may be a ring-opening polymer or an addition polymer, and is represented by heat resistance, low dielectric constant characteristics, low leakage current characteristics, high breakdown voltage characteristics, and the like.
- a ring-opening polymer is preferable from the viewpoint of excellent electrical characteristics and low water absorption.
- the polymer of this invention may copolymerize the monomer represented by the said General formula (1), and the monomer copolymerizable with this.
- the copolymerizable monomer is appropriately selected depending on the use of the polymer.
- the proportion of the monomer represented by the general formula (1) among all monomers used for obtaining the polymer can be arbitrarily selected according to the purpose of producing the polymer. Considering the balance of electrical characteristics typified by dielectric constant, low leakage current, high breakdown voltage, etc., low water absorption, high adhesion and compatibility with various materials, 5 to 90 mol% is preferable, 10 to 80 mol% is more preferable.
- the weight average molecular weight of the polymer of the present invention can be arbitrarily selected depending on the production purpose of the polymer, but is usually 1,000 to 1,000,000, preferably 1,500 to 500,000, more preferably. Is from 2,000 to 50,000.
- the weight average molecular weight (Mw) of the polymer is a value determined as a polystyrene equivalent value by gel permeation chromatography (GPC). When the Mw of the polymer is within the above range, the heat resistance and the solubility in a polar solvent are excellent.
- the polymer of the present invention is obtained by (i) homopolymerizing one of the monomers represented by the general formula (1), and (ii) a single monomer represented by the general formula (1). (Iii) at least one monomer represented by the general formula (1) and at least any other monomer copolymerizable therewith Any of those obtained by copolymerizing one kind may be used.
- cyclic olefin monomers having a protic polar group (a), other than protic polar groups excluding the monomer represented by the general formula (1)
- the monomer (d) may have a protic polar group or other polar group, or may not have a polar group at all.
- the polymer obtained by polymerizing the monomer represented by the general formula (1) is preferably a polymer having a protic polar group from the viewpoint of excellent heat resistance and adhesion. More preferably, it is a polymer having a protic polar group obtained by copolymerizing the monomer represented by the general formula (1) and the monomer (a).
- a polymer having a protic polar group obtained by copolymerizing the monomer represented by the general formula (1) and the monomer (a) is, for example, a monomer (b). It may be a polymer obtained by polymerizing other monomers such as (d).
- the monomer represented by the general formula (1) include N- (1-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (2-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylbutyl) -bicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylhexyl) -bicyclo [2.2.1] P
- the protic polar group is an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or 16 of the periodic table.
- a group containing 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 resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.
- cyclic olefin monomer (a) having a protic polar group examples include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 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, 8-hydroxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 .
- cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.
- cyclic olefin monomer (b) having a polar group other than the protic polar group excluding the monomer represented by the general formula (1) include an ester group and the general formula (1).
- examples thereof include N-substituted imide groups excluding monomers, cyano groups, and cyclic olefins having a halogen atom.
- Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 3,6 .
- dodec-4-ene 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 3,6 .
- Examples of the cyclic olefin having an N-substituted imide group excluding the monomer represented by the general formula (1) include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (endo-bicyclo [2.2.1] hept-5-ene-2,3-diyldicarbonyl) methyl aspartate and the like can be mentioned.
- 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 .
- cyclic olefin having a halogen atom examples 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.
- the cyclic olefin monomer (b) having a polar group other than the protic polar group excluding the monomer represented by the general formula (1) may be used alone or in combination of two or more. It may be used.
- 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.
- the monomer (d) other than the cyclic olefin examples 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, ⁇ -olefins having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; Non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-oc
- a protic polar group is introduced into a polymer not having a protic polar group using a known modifier, and hydrogenated as desired. It can be obtained also by the method of performing.
- hydrogenation may be performed on the polymer before introduction of the protic polar group.
- the polymer having a protic polar group may be further modified to further introduce a protic polar group.
- a polymer having no protic polar group can be obtained by copolymerizing the monomer represented by the general formula (1) and any combination of the monomers (b) to (d). Can do.
- 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 polymer using these modifiers may be performed according to a conventional method, and is usually performed in the presence of a radical generator.
- the polymer of the present invention will be described separately for the case of being a ring-opening polymer and the case of being an addition polymer.
- the ring-opening polymer is obtained by opening at least one of the monomers represented by the general formula (1) and a copolymerizable monomer used as necessary in the presence of a metathesis reaction catalyst. It can be produced by metathesis polymerization.
- the metathesis reaction catalyst may be any catalyst as long as it is a group 3-11 transition metal compound in the periodic table and performs ring-opening metathesis polymerization of the polymerization unit represented by the general formula (1).
- a metathesis reaction catalyst those described in Olefin Metathesis and Metathesis Polymerization (KJ Ivinand JC Mol, Academic Press, San Diego 1997) can be used.
- metathesis reaction catalyst examples include a group 3-11 transition metal-carbene complex catalyst of the periodic table. Among these, use of a ruthenium carbene complex catalyst is preferable.
- Examples of the Group 3-11 transition metal-carbene complex catalyst of the periodic table include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.
- tungsten alkylidene complex catalysts W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) ( OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2 , 6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2 W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and the like.
- molybdenum alkylidene complex catalyst Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2, 6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2 Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe2Ph) (OCMe 2 CF 3) 2, Mo (N -2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2
- rhenium alkylidene complex catalyst Re (CBu t) (CHBu t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2- Bu t C 6 H 4) 2 , Re (CBu t) (CHBu t) (OCMe 2 CF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu t ) (O-2,6-Me 2 C 6 H 3 ) 2 and the like.
- ruthenium carbene complex catalyst examples include compounds represented by the following general formula (2) or general formula (3).
- ⁇ CR 3 R 4 and ⁇ C ⁇ CR 3 R 4 are carbene compounds containing a carbene carbon at the reaction center.
- R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom,
- the carbene compound may or may not contain a heteroatom.
- L 1 represents a heteroatom-containing carbene compound
- L 2 represents a heteroatom-containing carbene compound or any neutral electron-donating compound.
- the heteroatom-containing carbene compound refers to a compound containing a carbene carbon and a heteroatom.
- L 1 and L 2 or L 1 is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.
- L 3 and L 4 each independently represent an arbitrary anionic ligand. Also, 2, 3, 4, 5 or 6 of R 3 , R 4 , L 1 , L 2 , L 3 and L 4 are bonded to each other to form a multidentate chelating ligand. May be.
- Specific examples of heteroatoms include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.
- the anionic (anionic) ligands L 3 and L 4 are ligands having a negative charge when separated from the central metal, for example, Halogen atoms such as fluorine, chlorine, bromine and iodine; hydrocarbons containing oxygen such as diketonate, alkoxy, aryloxy and carboxyl groups; substituted with halogen atoms such as cyclopentadienyl chloride And alicyclic hydrocarbon groups.
- Halogen atoms such as fluorine, chlorine, bromine and iodine
- hydrocarbons containing oxygen such as diketonate, alkoxy, aryloxy and carboxyl groups
- halogen atoms such as cyclopentadienyl chloride And alicyclic hydrocarbon groups.
- a halogen atom is preferable and a chlorine atom is more preferable.
- L 2 When L 2 is a neutral electron donating compound, L 2 may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable.
- Examples of the ruthenium complex catalyst represented by the general formula (2) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl).
- Ruthenium bonded with two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Carbene complex; and the like.
- Examples of the ruthenium carbene complex catalyst represented by the general formula (3) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butyl). Vinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.
- the ring-opening polymerization using a metathesis reaction catalyst can be performed in a solvent or without a solvent.
- the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.
- the solvent used is not particularly limited as long as it dissolves the polymer produced and does not inhibit the polymerization reaction.
- the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers
- Ketones methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like.
- aromatic hydrocarbons alicyclic hydrocarbons, ethers, ketones or esters is preferable.
- the concentration of the monomer composition in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. If the concentration of the monomer composition is less than 1% by weight, the productivity of the polymer may be deteriorated. If it exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation becomes difficult. There is.
- the metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved.
- the solvent for preparing the catalyst solution include the same solvents as those used for the polymerization reaction.
- a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer.
- molecular weight modifiers include ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used.
- a polymer having a desired molecular weight can be obtained by using 0.05 to 50 mol% of a molecular weight modifier with respect to the monomer composition containing the polymerization unit represented by the general formula (1). it can.
- the polymerization temperature is not particularly limited, but is usually ⁇ 100 ° C. to + 200 ° C., preferably ⁇ 50 ° C. to + 180 ° C., more preferably ⁇ 30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C.
- the polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.
- the addition polymer is a known addition polymerization catalyst, at least one of the monomers represented by the general formula (1), and a copolymerizable monomer used as necessary. It can be obtained by polymerization using a polymerization catalyst such as a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000 as a molar ratio of the metal compound to the monomer in the polymerization catalyst.
- the hydrogenated product of the present invention is obtained by hydrogenating a carbon-carbon double bond contained in the main chain of the ring-opening polymer of the present invention.
- the ratio of hydrogenated carbon-carbon double bonds is usually 50% or more, and preferably 70% or more from the viewpoint of heat resistance. % Or more is more preferable, and 95% or more is still more preferable.
- Hydrogenation ratio of the hydrogenated product may, for example, carbon in the 1 H-NMR spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, carbon in the 1 H-NMR spectrum of the hydrogenated product - carbon double It can obtain
- the hydrogenation reaction can be performed, for example, by converting a carbon-carbon double bond in the main chain of the ring-opened polymer into a saturated single bond using hydrogen gas in the presence of a hydrogenation catalyst.
- the hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be appropriately used.
- homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc.
- Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above-mentioned ring-opening metathesis reaction catalyst, JP-A-7-2929, JP-A-7-149823 Noble metal complexes comprising ruthenium compounds described in JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Medium; and the like.
- heterogeneous catalyst examples include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.
- rhodium, ruthenium, and the like can be selectively hydrogenated from carbon-carbon double bonds in the polymer without causing side reactions such as modification of the functional group contained in the ring-opening polymer.
- a noble metal complex catalyst and a palladium supported catalyst such as palladium / carbon is preferred, and the use of a ruthenium carbene complex catalyst or a palladium supported catalyst is more preferred.
- the aforementioned ruthenium carbene complex catalyst can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.
- a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as ⁇ -olefin is added to activate the catalyst. Then, a method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method for improving the activity by adding a base such as triethylamine or N, N-dimethylacetamide.
- the hydrogenation reaction is usually performed in an organic solvent.
- an organic solvent it can select suitably by the solubility of the hydride to produce
- the organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis reaction catalyst from the reaction solution without replacing the solvent.
- the conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used.
- the amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. .
- the reaction temperature is usually ⁇ 10 ° C. to + 250 ° C., preferably ⁇ 10 ° C. to + 210 ° C., more preferably 0 ° C. to + 200 ° C. At a temperature lower than this range, the reaction rate becomes slow. Conversely, at a high temperature, a side reaction tends to occur.
- the pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, and more preferably 0.1 to 6.0 MPa.
- the time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate.
- the reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 90% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. 95% or more can be hydrogenated.
- the polymer and hydrogenated product of the present invention obtained as described above are excellent in electrical characteristics such as heat resistance, low dielectric constant characteristics, low leakage current characteristics and high breakdown voltage characteristics, low water absorption and adhesion, It is highly reliable, has high transparency, and is excellent in pattern formation by development. Therefore, the polymer and hydrogenated product of the present invention are made of heat-resistant optical component materials such as plastic lenses, spherical lenses, non-spherical lenses, copier lenses, video camera converter lenses, optical disk pickup lenses, and vehicle component lenses; Materials for electronic parts such as sealing materials, semiconductor under film materials, semiconductor protective film materials, liquid crystal sealing materials, circuit substrate materials, circuit protection materials, planarizing film materials, electrical insulating film materials, etc. It can use suitably for the use of.
- heat-resistant optical component materials such as plastic lenses, spherical lenses, non-spherical lenses, copier lenses, video camera converter lenses, optical disk pickup lenses, and vehicle component lenses
- Materials for electronic parts such as sealing materials, semiconductor under film materials, semiconductor protective film materials,
- the resin composition of the present invention comprises a polymer obtained by polymerizing the monomer represented by the above general formula (1) and / or a hydrogenated product thereof (A) (hereinafter simply referred to as “polymer (A)”). And a solvent (B).
- the solvent (B) used in the present invention is not particularly limited as long as it can dissolve the components contained in the resin composition satisfactorily.
- methanol, ethanol, propanol, butanol, 3-methoxy-3- Alcohols such as methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol Glycol ethers such as ethyl methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA); benzene, toluene, Aromatic hydrocarbons such as silene; ketones such as methyl ethyl ketone, cyclopentanone, cycl
- diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone and N-methyl-2-pyrrolidone are preferable, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate (PGMEA) are more preferable, and diethylene glycol ethyl Methyl ether is particularly preferred.
- solvents (B) may be used alone or in combination of two or more.
- the content of the solvent (B) in the resin composition of the present invention is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 parts by weight of the polymer (A). Is in the range of 100 to 1,000 parts by weight.
- the resin composition of this invention further contains a crosslinking agent (C).
- the crosslinking agent (C) include those that form a crosslinked structure between the crosslinking agent molecules by heating, and those that react with the polymer (A) to form a crosslinked structure between the resin molecules.
- a compound having two or more reactive groups include an amino group, a carboxy 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.
- the epoxy group is preferably a terminal epoxy group or an alicyclic epoxy group, and more preferably an alicyclic epoxy group.
- the molecular weight of the crosslinking agent (C) is not particularly limited, but is usually 100 to 100,000, preferably 300 to 50,000, more preferably 500 to 10,000.
- crosslinking agent (C) 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 which may have a methylol group such as ''-(hexaalkoxyalkyl) melamine, an imino group or the like (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212) My Coat 506 " ⁇ End Cymel series, such as Industrial Co
- the epoxy compound examples include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having cyclohexane skeleton and terminal epoxy group.
- 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” (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries, Ltd.) Manufactured by Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound Epoxy compounds having no alicyclic structure
- crosslinking agent (C) a polyfunctional epoxy compound having two or more epoxy groups is preferable, and the resin film obtained by using the resin composition of the present invention is excellent in heat-resistant shape retention.
- a polyfunctional epoxy compound having a ring structure and having 3 or more epoxy groups is particularly preferred.
- These crosslinking agents can be used alone or in combination of two or more.
- the content of the crosslinking agent (C) in the resin composition of the present invention is not particularly limited, taking into consideration the degree of heat resistance required when a pattern is provided on a resin film obtained using the resin composition of the present invention. However, it is usually 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, most preferably 25 parts per 100 parts by weight of the polymer (A). ⁇ 75 parts by weight. If the crosslinking agent (C) is too much or too little, the heat resistance of the resulting resin film tends to decrease.
- the resin composition of the present invention further contains a radiation sensitive compound (D).
- the radiation-sensitive compound (D) used in the present invention is a compound that can cause a chemical reaction by irradiation with radiation such as ultraviolet rays or electron beams.
- the radiation sensitive compound (D) is preferably one that can control the alkali solubility of the resin film formed from the resin composition, and it is particularly preferable to use a photoacid generator.
- Examples of the radiation-sensitive compound (D) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.
- azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.
- 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 (2.0 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 (D) in the resin composition of the present invention is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 10 parts by weight with respect to 100 parts by weight of the polymer (A). It is in the range of ⁇ 60 parts by weight. If the content of the radiation-sensitive compound (D) is within this range, when a resin film made of the resin composition of the present invention is formed on an arbitrary substrate and patterned, a radiation irradiated part and a radiation non-irradiated part This is preferable because the difference in solubility in the developer becomes large, the radiation sensitivity increases, and patterning by development is easy.
- the resin composition used in the present invention is a sensitizer, a surfactant, a latent acid generator, an antioxidant, a coupling agent or a derivative thereof, light, if desired, as long as the effects of the present invention are not inhibited. It may contain other compounding agents such as stabilizers, antifoaming agents, pigments, dyes, fillers, and the like.
- 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.
- the resin composition of the present invention preferably contains a surfactant.
- 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
- the resin composition of the present invention preferably contains an acidic compound.
- the acidic compound is not particularly limited as long as it has an acidic group, and aliphatic compounds, aromatic compounds, heterocyclic compounds, and the like can be used.
- the acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group. It is done. Among these, a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable.
- acidic compounds 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 ethanedioic acid.
- oxalic acid propanedioic acid (also referred to as “malonic acid”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid, hexanedioic acid (also referred to as “adipic acid”) ), 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-buta Diol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, ali
- 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 resin composition of the present invention preferably contains a coupling agent or a derivative thereof.
- a coupling agent or derivative thereof a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom can be used.
- 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-hepty
- the resin composition of the present invention preferably contains a light stabilizer.
- Light stabilizers include UV absorbers such as benzophenone, salicylic acid ester, benzotriazole, cyanoacrylate, and metal complex salts, hindered amine (HALS), etc. that capture radicals generated by light, etc. But you can.
- HALS is a compound having a piperidine structure, and is preferable because the resin composition of the present invention is less colored and stable.
- 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 method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition of the present invention may be mixed by a 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 constituting the resin composition in a solvent. 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 constituting the resin composition of the present invention in a solvent may follow 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 a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 ⁇ m.
- the solid content concentration of the resin composition of the present invention 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.
- the resin film of the present invention can be obtained by forming it on a substrate using the above-described resin composition of the present invention.
- a printed wiring substrate for example, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used.
- the substrate surface may be physically and / or chemically surface treated, and may have a multiple layer structure in which other thin films are formed on the substrate surface.
- 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 application method is, for example, a method in which a resin composition is applied on a substrate and then dried by heating to remove the solvent.
- 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 contained in the resin composition, 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, 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 contained in the resin composition, 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.
- the resin film when the resin composition contains a crosslinking agent (C), the resin film can be subjected to a crosslinking reaction after the resin film is formed on the substrate.
- the resin film formed on the substrate may be cross-linked by appropriately selecting the method depending on the type of the cross-linking agent (C), 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 according to the size and thickness of the resin film, the equipment used, and the like.
- the oven when using a hot plate, 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 resin composition contains a radiation-sensitive compound (D)
- the patterned resin film formed on the substrate is irradiated with actinic radiation on the resin film formed from the resin composition to form a latent image pattern.
- the developer is brought into contact with a resin film having a latent image pattern to reveal the pattern.
- the actinic radiation is not particularly limited as long as it can activate the radiation sensitive compound (D) and change the alkali solubility of the resin composition containing the radiation sensitive compound (D).
- 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 used as a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern.
- ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like.
- 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; and the like 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. It is appropriately selected within a range of 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.
- 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 heating 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 resin film of the present invention is obtained using the above-described resin composition containing the polymer of the present invention and a hydrogenated product, heat resistance, low dielectric constant characteristics, low leakage current characteristics, and high dielectric breakdown It has excellent electrical characteristics such as voltage characteristics, low water absorption and adhesion, high reliability, high transparency, and excellent pattern formation by development. Therefore, a laminate comprising such a resin film of the present invention and a substrate, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components, particularly semiconductor devices.
- the polymerization conversion rate was calculated from the value obtained by measuring the residual amount of the monomer in the reaction solution using gas chromatography after the completion of the polymerization reaction.
- the hydrogenation rate was determined from the 1 H-NMR spectrum as the ratio of the hydrogenated carbon-carbon double bond moles to the carbon-carbon double bond moles before hydrogenation.
- the ratio of hydrogenated carbon-carbon double bonds was determined as mol% based on the pre-hydrogenation standard.
- ⁇ Weight average molecular weight / number average molecular weight> For weight average molecular weight and number average molecular weight, gel permeation chromatography (abbreviation: GPC, manufactured by Tosoh Corporation, model plate “HLC-8020”, TSKgel SuperH2000, TSKgel SuperH4000, TSKgel SuperH5000, used in combination) The molecular weight was calculated in terms of polystyrene. Tetrahydrofuran was used as the developing solvent.
- MIBK methyl isobutyl ketone
- the determination as to whether the polymer or hydrogenated product was dissolved in methyl isobutyl ketone (MIBK) was evaluated by measuring the light transmittance. This is based on the principle that as the number of insoluble particles increases, the light transmittance decreases due to light scattering of the particles. Therefore, it can be said that the higher the light transmittance, the better the solubility.
- the light transmittance was measured using a spectrophotometer (manufactured by JASCO Corporation, “V-570 (product name)”), and the light at 400 nm of a solution obtained by dissolving 1 part of a polymer or hydrogenated product in 100 parts of MIBK.
- the solubility was determined from the light transmittance of the polymer or hydrogenated MIBK solution as follows. ⁇ : The light transmittance of the solution is 95% or more (the difference from the light transmittance of MIBK is small and the solubility is good). X: The light transmittance of the solution is less than 95% (the difference from the light transmittance of MIBK is large and the solubility is poor).
- the silicon wafer which has a resin film Furthermore, it post-baked by heating at 230 degreeC for 60 minutes using oven, and obtained the silicon wafer which has a resin film. And the part from which the flat resin film of the silicon wafer center part was obtained was cut
- the water absorption was measured by the following method. That is, the water absorption measurement sample obtained above was 230 ° C. at 60 ° C./min using a temperature-programmed desorption gas analyzer (abbreviated as TDS, manufactured by Electronic Science Co., Ltd., model number “WA1000S / W”). The temperature was raised to 30 minutes and held for 30 minutes, and the amount of water detected per unit area was taken as the water absorption value. It can be said that the lower the water absorption value, the less the water is contained and the better the resin film having a high insulating property against water.
- TDS temperature-programmed desorption gas analyzer
- ⁇ Adhesion> [Preparation of samples for adhesion measurement] After spin-coating the resin compositions obtained in the following Examples and Comparative Examples on a 10 cm square glass substrate [Corning, Corning 1737 (product name)], pre-baking at 90 ° C. for 2 minutes using a hot plate. A resin film having a thickness of 2.5 ⁇ m was formed. Next, 10 strip-shaped slits (corresponding to spaces) through which light passes are arranged in parallel, and the width between one slit and the adjacent slit (corresponding to a line) of the slit is the slit width. Through the same mask, exposure was performed for a desired time with light having a desired intensity sufficient to form a pattern.
- the slit width and the width between one of the slits and the adjacent slit are 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 10 ⁇ m, 25 ⁇ m, and 50 ⁇ m, respectively.
- a sample using a mask was prepared.
- the exposed resin film was developed with a paddle method for 60 seconds at 23 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution as a developer, and then with ultrapure water for 30 seconds. Rinse.
- the paddle method is a method in which a developer is placed on a resin film.
- a resin film having a pattern (line and space pattern) on which a mask pattern was transferred was produced on a glass substrate.
- the resin compositions obtained in the following examples and comparative examples have positive radiation sensitivity. Therefore, in the resin film, a portion corresponding to the slit portion of the mask is a portion where the resin film is removed. In this case, this portion is called a space portion. On the other hand, a portion between one slit of the mask and a slit immediately adjacent thereto is a portion where the resin film is left, and this portion is called a line portion. And the glass substrate in which the resin film which has the obtained pattern was formed in this way was made into the adhesiveness measurement sample.
- the adhesion was measured by the following method. That is, the adhesiveness measurement was performed by observing the adhesiveness measurement sample obtained above using an optical microscope and confirming whether or not the line part was peeled off from the substrate. If the line part does not peel off, it can be said that adhesion is high. In addition, when the line part was peeled off, it was confirmed to what extent the maximum line part had peeling. The line portion is more easily peeled off from the substrate as the width is smaller. Therefore, when peeling of the line portion from the substrate is confirmed, the smaller the maximum width of the line portion where peeling is confirmed (the width value of the largest width among the line portions where peeling is confirmed). It can be said that the adhesion is high.
- Example 1 N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 100 parts, 1,5-hexadiene 2 parts, (1,3-dimesityl imidazoline -2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium chloride (synthesized by the method described in Org. Lett., Vol. 1, page 953, 1999), and 400 parts of diethylene glycol methyl ethyl ether Then, it was charged into a glass pressure-resistant reactor substituted with nitrogen and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution of polymer A1.
- the resulting polymer A1 had a polymerization conversion rate of 99.6%, a weight average molecular weight of 5,660, a number average molecular weight of 3,510, and a molecular weight distribution of 1.49.
- Methyl isobutyl ketone (MIBK) solubility of the polymer A1 was evaluated. The evaluation results are shown in Table 1. Polymer A1 was soluble in MIBK at 25 ° C.
- Example 2 The polymerization reaction liquid of the polymer A1 obtained in Example 1 was put in an autoclave and a hydrogenation reaction was performed by stirring at 150 ° C. and a hydrogen pressure of 4 MPa for 5 hours to obtain a hydrogenated product A2.
- the resulting hydrogenated product A2 had a weight average molecular weight of 7,010, a number average molecular weight of 4,590, a molecular weight distribution of 1.53, and a hydrogenation rate of 99.8%.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A2 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A2 was soluble in MIBK at 25 ° C.
- Example 3 Addition of N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide by a known method described in JP-A-2006-016606 Combined A3 was obtained.
- the polymerization conversion rate of the addition polymer A3 was 78.3%, the weight average molecular weight was 75,400, and the number average molecular weight was 36,200.
- the methyl isobutyl ketone (MIBK) solubility of the polymer A3 was evaluated. The evaluation results are shown in Table 1. Polymer A3 was soluble in MIBK at 25 ° C.
- Example 4 Instead of N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept A polymerization reaction solution was obtained in the same manner as in Example 1 except that -5-ene-2,3-dicarboximide was used, and the polymerization reaction solution thus obtained was used in the same manner as in Example 2. By performing a hydrogenation reaction, a hydrogenated product A4 was obtained.
- the resulting hydrogenated product A4 had a polymerization conversion rate of 99.5%, a weight average molecular weight of 7,140, a number average molecular weight of 4,680, a molecular weight distribution of 1.53, and a hydrogenation rate of 99.8%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A4 was evaluated. The evaluation results are shown in Table 1. Hydrogenated A4 was soluble in MIBK at 25 ° C.
- Example 5 instead of N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyltridodecyl) -bicyclo [2.2.1] A polymerization reaction solution was obtained in the same manner as in Example 1 except that hept-5-ene-2,3-dicarboximide was used, and the same polymerization reaction solution as in Example 2 was obtained. Thus, a hydrogenation reaction was performed to obtain a hydrogenated product A5.
- the resulting hydrogenated product A5 had a polymerization conversion rate of 99.5%, a weight average molecular weight of 7,250, a number average molecular weight of 4,700, a molecular weight distribution of 1.54, and a hydrogenation rate of 99.7%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A5 was evaluated. The evaluation results are shown in Table 1. Hydrogenated A5 was soluble in MIBK at 25 ° C.
- Example 6 Instead of 100 parts of N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1 ] 80 parts hept-5-ene-2,3-dicarboximide and 8-hydroxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ]
- a polymerization reaction solution was obtained in the same manner as in Example 1 except that 20 parts of dodec-3-ene was used, and the polymerization reaction solution thus obtained was used in the same manner as in Example 2.
- a hydrogenated product A6 was obtained.
- the resulting hydrogenated product A6 had a polymerization conversion rate of 99.6%, a weight average molecular weight of 6,900, a number average molecular weight of 4,570, a molecular weight distribution of 1.51, and a hydrogenation rate of 99.9%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A6 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A6 was soluble in MIBK at 25 ° C.
- Example 7 Instead of 100 parts of N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1 ] 60 parts hept-5-ene-2,3-dicarboximide, and 8-hydroxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] Except for using 40 parts of dodec-3-ene, a polymerization reaction solution was obtained in the same manner as in Example 1, and the polymerization reaction solution thus obtained was used in the same manner as in Example 2. By performing a hydrogenation reaction, a hydrogenated product A7 was obtained.
- the resulting hydrogenated product A7 had a polymerization conversion rate of 99.7%, a weight average molecular weight of 6,780, a number average molecular weight of 4,450, a molecular weight distribution of 1.52, and a hydrogenation rate of 99.9%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A7 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A7 was soluble in MIBK at 25 ° C.
- the resulting hydrogenated product A8 had a polymerization conversion of 99.6%, a weight average molecular weight of 6,960, a number average molecular weight of 4,400, a molecular weight distribution of 1.58, and a hydrogenation rate of 99.8%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A8 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A8 was insoluble in MIBK at 25 ° C.
- the resulting hydrogenated product A9 had a polymerization conversion rate of 99.8%, a weight average molecular weight of 6,850, a number average molecular weight of 4,490, a molecular weight distribution of 1.53, and a hydrogenation rate of 99.7%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A9 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A9 was insoluble in MIBK at 25 ° C.
- the resulting hydrogenated product A10 had a polymerization conversion of 99.7%, a weight average molecular weight of 6,950, a number average molecular weight of 4,630, a molecular weight distribution of 1.50, and a hydrogenation rate of 99.7%. there were.
- Methyl isobutyl ketone (MIBK) solubility of the hydrogenated product A10 was evaluated. The evaluation results are shown in Table 1. Hydrogenated product A10 was insoluble in MIBK at 25 ° C.
- Example 8 100 parts by weight of the hydrogenated product A6 obtained in Example 6 as the polymer (A), 550 parts by weight of diethylene glycol ethyl methyl ether (EDM) as the solvent (B), and epoxidized butanetetracarboxylic acid tetrakis ( 3-cyclohexenylmethyl) -modified ⁇ -caprolactone (alicyclic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.) 50 parts by weight, silicone surfactant (Shin-Etsu) as surfactant 0.05 parts by weight of “KP-341 (product name)” manufactured by Kagaku Kogyo Co., Ltd.) was mixed and dissolved, and then filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 ⁇ m to prepare a resin composition 1. . Using this resin composition 1, water absorption was evaluated. The results are shown in Table 2.
- Example 8 was the same as Example 8 except that hydrogenated product A7 (Example 9), hydrogenated product A9 (Comparative Example 4), and hydrogenated product A10 (Comparative Example 5) were used instead of hydrogenated product A6.
- Resin compositions 2 to 4 were prepared as described above. Using these resin compositions 2 to 4, water absorption was evaluated. The results are shown in Table 2.
- Example 10 100 parts by weight of the hydrogenated product A6 obtained in Example 6 as the polymer (A), 550 parts by weight of diethylene glycol ethyl methyl ether (EDM) as the solvent (B), 1,2-quinonediazide compound as the radiation sensitive compound (D) 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) as 30 parts by weight of the condensate and 0.05 part by weight of a silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., “KP-341 (product name)”) as a surfactant are mixed and dissolved, and then the pore size is 0.45 ⁇ m.
- a resin composition 5 was prepared by filtration through a polytetrafluoroethylene filter. Using this resin composition 5, the adhesion was evaluated. The results are shown in Table 3.
- Example 10 was the same as Example 10 except that hydrogenated product A7 (Example 11), hydrogenated product A9 (Comparative Example 6), and hydrogenated product A10 (Comparative Example 7) were used instead of the hydrogenated product A6.
- Resin compositions 6 to 8 were prepared as described above. Using these resin compositions 6 to 8, adhesion was evaluated. The results are shown in Table 3.
- a polymer containing polymerized units of the monomer represented by the general formula (1) was obtained. Further, a hydrogenated product obtained by hydrogenating a ring-opening polymer having a repeating unit obtained by ring-opening polymerization of the monomer represented by the general formula (1) was obtained. It can be confirmed that the obtained polymer and its hydrogenated product have high solubility in MIBK which is a polar solvent and can be used for a wide range of applications (Examples 1 to 7).
- the resin composition having a polymer (hydrogenated product) obtained by polymerizing the monomer represented by the general formula (1) has low water absorption, and thus has an insulating property. Resin films that can be suitably used for a wide range of applications due to excellent and high adhesiveness can be produced (Examples 8 to 11).
Abstract
Description
本発明の重合体は、前記一般式(1)で表される単量体の重合単位を含んでなる重合体である。本発明の重合体は、開環重合体であっても、あるいは付加重合体であってもよいが、耐熱性、低誘電率特性、低リーク電流特性及び高絶縁破壊電圧特性などに代表される電気特性並びに低吸水性等により優れるという点より、開環重合体であることが好ましい。
前記重合体を得るために使用する全単量体中、一般式(1)で表される単量体の割合は、重合体の製造目的によって任意に選択することができるが、耐熱性、低誘電率、低リーク電流、高絶縁破壊電圧などに代表される電気特性、低吸水性、高密着性及び種々の材料との相溶性のバランスを考慮すると、5~90モル%が好ましく、10~80モル%がより好ましい。
本発明において、前記一般式(1)で表される単量体を重合してなる重合体は、耐熱性および密着性に優れるという点より、プロトン性極性基を有する重合体であることが好ましく、前記一般式(1)で表される単量体と、単量体(a)とを共重合してなる、プロトン性極性基を有する重合体であることがより好ましい。なお、一般式(1)で表される単量体と、単量体(a)とを共重合してなる、プロトン性極性基を有する重合体は、所望により、例えば単量体(b)~(d)などの、その他の単量体を共に重合して得られる重合体であっても構わない。
本発明において、プロトン性極性基を有する環状オレフィン樹脂に結合しているプロトン性極性基の数に特に限定はなく、また、相異なる種類のプロトン性極性基が含まれていてもよい。
エステル基を有する環状オレフィンとしては、例えば、5-アセトキシビシクロ[2.2.1]ヘプト-2-エン、5-メトキシカルボニルビシクロ[2.2.1]ヘプト-2-エン、5-メチル-5-メトキシカルボニルビシクロ[2.2.1]ヘプト-2-エン、9-アセトキシテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-エトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-n-プロポキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-イソプロポキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-n-ブトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-メトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-エトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-n-プロポキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-イソプロポキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-n-ブトキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-(2,2,2-トリフルオロエトキシカルボニル)テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-(2,2,2-トリフルオロエトキシカルボニル)テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン等が挙げられる。
シアノ基を有する環状オレフィンとしては、例えば、9-シアノテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-シアノテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、5-シアノビシクロ[2.2.1]ヘプト-2-エン等が挙げられる。
ハロゲン原子を有する環状オレフィンとしては、例えば、9-クロロテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチル-9-クロロテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン等が挙げられる。
これらの一般式(1)で表される単量体を除くプロトン性極性基以外の極性基を有する環状オレフィン単量体(b)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらの極性基を持たない環状オレフィン単量体(c)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらの環状オレフィン以外の単量体(d)は、それぞれ単独で又は2種以上を組み合わせて用いることができる。
プロトン性極性基を有しない重合体は、一般式(1)で表される単量体と、前記単量体(b)~(d)の任意の組み合わせと、を共重合することによって得ることができる。
このような化合物の具体例としては、アクリル酸、メタクリル酸、アンゲリカ酸、チグリン酸、オレイン酸、エライジン酸、エルカ酸、ブラシジン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、アトロパ酸、ケイ皮酸等の不飽和カルボン酸;アリルアルコール、メチルビニルメタノール、クロチルアルコール、メタリルアルコール、1-フェニルエテン-1-オール、2-プロペン-1-オール、3-ブテン-1-オール、3-ブテン-2-オール、3-メチル-3-ブテン-1-オール、3-メチル-2-ブテン-1-オール、2-メチル-3-ブテン-2-オール、2-メチル-3-ブテン-1-オール、4-ペンテン-1-オール、4-メチル-4-ぺンテン-1-オール、2-ヘキセン-1-オール等の不飽和アルコール;等が挙げられる。
これら変性剤を用いた重合体の変性反応は、常法に従えばよく、通常、ラジカル発生剤の存在下で行われる。
開環重合体は、前記一般式(1)で表される単量体のうち少なくとも1種、及び必要に応じて用いられる共重合可能な単量体を、メタセシス反応触媒の存在下に開環メタセシス重合することにより製造することができる。
本発明の樹脂組成物は、上述した一般式(1)で表される単量体を重合してなる重合体及び/又はその水素添加物(A)(以下、単に「重合体(A)」とする。)と、溶剤(B)とを有する。
この中でも、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、シクロペンタノン、N-メチル-2-ピロリドンが好ましく、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート(PGMEA)がより好ましく、ジエチレングリコールエチルメチルエーテルが特に好ましい。
かかる反応性基としては、例えば、アミノ基、カルボキシ基、水酸基、エポキシ基、イソシアネート基等が挙げられ、より好ましくはアミノ基、エポキシ基及びイソシアネート基であり、更に好ましくはエポキシ基である。エポキシ基は、末端エポキシ基、脂環式エポキシ基が好ましく、脂環式エポキシ基がより好ましい。
これらの中でも、1,2-ナフトキノンジアジド-5-スルホン酸クロライドとフェノール性水酸基を有する化合物との縮合物が好ましく、1,1,3-トリス(2,5-ジメチル-4-ヒドロキシフェニル)-3-フェニルプロパン(1モル)と1,2-ナフトキノンジアジド-5-スルホン酸クロライド(2.0モル)との縮合物がより好ましい。
これらの感放射線化合物は、それぞれ単独で又は2種以上を組み合わせて用いることができる。
界面活性剤は、ストリエーション(塗布筋あと)の防止、現像性の向上等の目的で使用される。その具体例としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類;ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアリールエーテル類;ポリオキシエチレンジラウレート、ポリオキシエチレンジステアレート等のポリオキシエチレンジアルキルエステル類等のノニオン系界面活性剤;フッ素系界面活性剤;シリコーン系界面活性剤;メタクリル酸共重合体系界面活性剤;アクリル酸共重合体系界面活性剤;等が挙げられる。
酸性化合物としては、酸性基を有するものであればよく、特に限定されないが、脂肪族化合物、芳香族化合物、複素環化合物等が使用できる。酸性基は、酸性の官能基であればよく、その具体例としては、スルホン酸基、リン酸基等の強酸性基;カルボキシ基、チオール基及びカルボキシメチレンチオ基等の弱酸性基;が挙げられる。これらの中でも、カルボキシ基、チオール基またはカルボキシメチレンチオ基が好ましく、カルボキシ基が特に好ましい。酸性化合物の具体例としては、メタン酸、エタン酸、プロパン酸、ブタン酸、ペンタン酸、ブタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、グリコール酸、グリセリン酸、エタン二酸(「シュウ酸」ともいう。)、プロパン二酸(「マロン酸」ともいう。)、ブタン二酸(「コハク酸」ともいう。)、ペンタン二酸、ヘキサン二酸(「アジピン酸」ともいう。)、1、2―シクロヘキサンジカルボン酸、2-オキソプロパン酸、2-ヒドロキシブタン二酸、2-ヒドロキシプロパントリカルボン酸、メルカプトコハク酸、ジメルカプトコハク酸、2,3-ジメルカプト-1-プロパノール、1,2,3-トリメルカプトプロパン、2,3,4-トリメルカプト-1-ブタノール、2,4-ジメルカプト-1,3-ブタンジオール、1,3,4-トリメルカプト-2-ブタノール、3,4-ジメルカプト-1,2-ブタンジオール、1,5-ジメルカプト-3-チアペンタン等の脂肪族化合物;
これらの中でも、樹脂組成物から形成される樹脂膜を、基板に対する密着性が良好なものとすることができるという観点から、酸性基の数は、2つ以上であることが好ましく、2つが特に好ましい。
酸性基を2つ有する化合物としては、エタン二酸、プロパン二酸、ブタン二酸、ペンタン二酸、ヘキサン二酸、1,2―シクロヘキサンジカルボン酸、ベンゼン-1,2-ジカルボン酸(「フタル酸」ともいう。)、ベンゼン-1,3-ジカルボン酸(「イソフタル酸」ともいう。)、ベンゼン-1,4-ジカルボン酸(「テレフタル酸」ともいう。)ビフェニル-2,2’-ジカルボン酸、2-(カルボキシメチル)安息香酸、3-(カルボキシメチル)安息香酸、4-(カルボキシメチル)安息香酸、2-メルカプト安息香酸、4-メルカプト安息香酸、2-メルカプト-6-ナフタレンカルボン酸、2-メルカプト-7-ナフタレンカルボン酸、1,2-ジメルカプトベンゼン、1,3-ジメルカプトベンゼン、1,4-ジメルカプトベンゼン、1,4-ナフタレンジチオール、1,5-ナフタレンジチオール、2,6-ナフタレンジチオール、2,7-ナフタレンジチオールの2つの酸性基を有する芳香族化合物;ピロール-2,3-ジカルボン酸、ピロール-2,4-ジカルボン酸、ピロール-2,5-ジカルボン酸、ピロール-3,4-ジカルボン酸、イミダゾール-2,4-ジカルボン酸-、イミダゾール-2,5-ジカルボン酸、イミダゾール-4,5-ジカルボン酸、ピラゾール-3,4-ジカルボン酸、ピラゾール-3,5-ジカルボン、チオフェン-2,3-ジカルボン酸、チオフェン-2,4-ジカルボン酸、チオフェン-2,5-ジカルボン酸、チオフェン-3,4-ジカルボン酸、チアゾール-2,4-ジカルボン酸、チアゾール-2,5-ジカルボン酸、チアゾール-4,5-ジカルボン酸、イソチアゾール-3,4-ジカルボン酸、イソチアゾール-3,5-ジカルボン酸、1,2,4-チアジアゾール-2,5-ジカルボン酸、1,3,4-チアジアゾール-2,5-ジカルボン酸、(5-メルカプト-1,2,4-チアジアゾール-3-イルチオ)酢酸、(5-メルカプト-1,3,4-チアジアゾール-2-イルチオ)酢酸、ピリジン-2,3-ジカルボン酸、ピリジン-2,4-ジカルボン酸、ピリジン-2,5-ジカルボン酸、ピリジン-2,6-ジカルボン酸、ピリジン-3,4-ジカルボン酸、ピリジン-3,5-ジカルボン酸、ピリダジン-3,4-ジカルボン酸、ピリダジン-3,5-ジカルボン酸、ピリダジン-3,6-ジカルボン酸、ピリダジン-4,5-ジカルボン酸、ピリミジン-2,4-ジカルボン酸、ピリミジン-2,5-ジカルボン酸、ピリミジン-4,5-ジカルボン酸、ピリミジン-4,6-ジカルボン酸、ピラジン-2,3-ジカルボン酸、ピラジン-2,5-ジカルボン酸、ピリジン-2,6-ジカルボン酸、トリアジン-2,4-ジカルボン酸の2つの酸性基を有する複素環化合物;が好ましい。
これらの化合物を使用することにより、樹脂組成物から形成される樹脂膜と基板との密着性がより高くなるという効果を得ることができる。
カップリング剤又はその誘導体としては、ケイ素原子、チタン原子、アルミニウム原子、ジルコニウム原子から選ばれる1つの原子を有し、該原子に結合したヒドロカルビルオキシ基又はヒドロキシ基を有する化合物等が使用できる。
カップリング剤又はその誘導体としては、例えば、
テトラメトキシシラン、テトラエトキシシラン、テトラ-n-プロポキシシラン、テトラ-i-プロポキシシラン、テトラ-n-ブトキシシランなどのテトラアルコキシシラン類、
メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、n-プロピルトリメトキシシラン、n-プロピルトリエトキシシラン、i-プロピルトリメトキシシラン、i-プロピルトリエトキシシラン、n-ブチルトリメトキシシラン、n-ブチルトリエトキシシラン、n-ペンチルトリメトキシシラン、n-ヘキシルトリメトキシシラン、n-ヘプチルトリメトキシシラン、n-オクチルトリメトキシシラン、n-デシルトリメトキシシラン、p-スチリルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、3-クロロプロピルトリメトキシシラン、3-クロロプロピルトリエトキシシラン、3,3,3-トリフルオロプロピルトリメトキシシラン、3,3,3-トリフルオロプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、2-ヒドロキシエチルトリメトキシシラン、2-ヒドロキシエチルトリエトキシシラン、2-ヒドロキシプロピルトリメトキシシラン、2-ヒドロキシプロピルトリエトキシシラン、3-ヒドロキシプロピルトリメトキシシラン、3-ヒドロキシプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、3-イソシアナートプロピルトリメトキシシラン、3-イソシアナートプロピルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、3-(メタ)アクリルオキシプロピルトリメトキシシラン、3-(メタ)アクリルオキシプロピルトリエトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-エチル(トリメトキシシリルプロポキシメチル)オキセタン、3-エチル(トリエトキシシリルプロポキシメチル)オキセタン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、ビス(トリエトキシシリルプロピル)テトラスルフィドなどのトリアルコキシシラン類、
ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ-n-プロピルジメトキシシラン、ジ-n-プロピルジエトキシシラン、ジ-i-プロピルジメトキシシラン、ジ-i-プロピルジエトキシシラン、ジ-n-ブチルジメトキシシラン、ジ-n-ペンチルジメトキシシラン、ジ-n-ペンチルジエトキシシラン、ジ-n-ヘキシルジメトキシシラン、ジ-n-ヘキシルジエトキシシラン、ジ-n-へプチルジメトキシシラン、ジ-n-ヘプチルジエトキシシラン、ジ-n-オクチルジメトキシシラン、ジ-n-オクチルジエトキシシラン、ジ-n-シクロヘキシルジメトキシシラン、ジ-n-シクロヘキシルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-メタクリルオキシプロピルメチルジメトキシシラン、3-アクリルオキシプロピルメチルジメトキシシラン、3-メタクリルオキシプロピルメチルジエトキシシラン、3-アクリルオキシプロピルメチルジエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシランなどのジアルコキシシラン類の他、
メチルトリアセチルオキシシラン、ジメチルジアセチルオキシシラン、商品名X-12-414、KBP-44(信越化学工業株式会社製)、217FLAKE、220FLAKE、233FLAKE、z6018(東レダウコーニング株式会社製)等のケイ素原子含有化合物;
(アセトアルコキシアルミウムジイソプロピレート)等のアルミニウム原子含有化合物;
(テトラ-n-プロポキシジルコニウム、テトラ-n-ブトキシジルコニウム、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス(エチルアセトアセテート)、ジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシステアレート)等のジルコニウム原子含有化合物;が挙げられる。
これらの化合物を使用することにより、樹脂組成物から形成される樹脂膜と基板との密着性がより高くなるという効果を得ることができる。
光安定剤は、ベンゾフェノン系、サリチル酸エステル系、ベンゾトリアゾール系、シアノアクリレート系、金属錯塩系等の紫外線吸収剤、ヒンダ-ドアミン系(HALS)等、光により発生するラジカルを捕捉するもの等のいずれでもよい。これらのなかでも、HALSはピペリジン構造を有する化合物で、本発明の樹脂組成物に対し着色が少なく、安定性が良いため好ましい。具体的な化合物としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、1,2,2,6,6-ペンタメチル-4-ピペリジル/トリデシル1,2,3,4-ブタンテトラカルボキシレート、ビス(1-オクチロキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート等が挙げられる。
混合の方法は特に限定されないが、樹脂組成物を構成する各成分を溶剤に溶解又は分散して得られる溶液又は分散液を混合するのが好ましい。これにより、本発明の樹脂組成物は、溶液又は分散液の形態で得られる。
本発明の樹脂膜は、上述した本発明の樹脂組成物を用いて基板上に形成させることによって得ることができる。
基板上に形成されたパターン化樹脂膜は、例えば、樹脂組成物が感放射線化合物(D)を含有する場合に、該樹脂組成物から形成された樹脂膜に活性放射線を照射して潜像パターンを形成し、次いで潜像パターンを有する樹脂膜に現像液を接触させることによりパターンを顕在化させて得ることができる。
潜像パターンを有する樹脂膜に現像液を接触させる方法としては、例えば、パドル法、スプレー法、ディッピング法等の方法が用いられる。現像条件としては、適宜選択すればよいが、現像温度は、通常、0~100℃、好ましくは5~55℃、より好ましくは10~30℃の範囲であり、現像時間は、通常、30~180秒間の範囲で適宜選択である。
更に、必要に応じて、感放射線化合物(D)を失活させるために、パターン化樹脂膜を有する基板全面に活性放射線を照射することもできる。活性放射線の照射には、上記潜像パターンの形成方法において例示した方法を利用できる。活性放射線の照射と同時に又は照射後に樹脂膜を加熱してもよい。加熱方法としては、例えば、基板をホットプレートやオーブン内で加熱する方法が挙げられる。加熱温度は、通常、100~300℃、好ましくは120~200℃の範囲である。
架橋は、上述した基板上に形成された樹脂膜の架橋と同様に行なえばよい。
なお、本実施例において、「部」及び「%」は、特に断りのない限り、それぞれ、「重量部」及び「重量%」である。
各特性は、以下の方法により評価する。
重合転化率は、重合反応終了後、ガスクロマトグラフィーを用いて反応液中の単量体の残存量を測定し、その値より算出した。
水素添加率は、1H-NMRスペクトルにより、水素添加された炭素-炭素二重結合モル数を水素添加前の炭素-炭素二重結合モル数に対する割合として求めた。本実施例では、水素添加前を基準として、水素添加された炭素-炭素二重結合の割合をモル%として求めた。
重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー(略称GPC、東ソー社製、型版「HLC-8020」、TSKgel SuperH2000、TSKgel SuperH4000、TSKgel SuperH5000の3種類のカラムを組み合わせて使用)を用い、ポリスチレン換算の分子量として算出した。なお、展開溶剤としては、テトラヒドロフランを用いた。
重合体又は水素添加物がメチルイソブチルケトン(MIBK)に溶解したか否かの判定は、光線透過率を測定することによって評価した。不溶の粒子が増えるほど、粒子の光散乱によって、光線透過率が減少する原理による。従って、光線透過率が高いほど溶解性に優れると言える。
光線透過率の測定は、分光光度計(日本分光社製、「V-570(製品名)」)を用いて、重合体又は水素添加物1部をMIBK100部で溶解した溶液の、400nmにおける光線透過率を測定することにより行なった。なお、測定に際しては、重合体又は水素添加物をMIBKで溶解した前記溶液の光線透過率を測定する前に、MIBK単独の液が光線透過率100%となるように前記分光光度計の基準化を行った。
重合体又は水素添加物のMIBK溶液の光線透過率から溶解性を以下のように判定した。
○:溶液の光線透過率が95%以上(MIBKの光線透過率との差が小さく、溶解性が良い。)
×:溶液の光線透過率が95%未満(MIBKの光線透過率との差が大きく、溶解性は悪い。)
〔吸水性測定用試料の作製〕
直径4インチ、厚さ0.52mmのシリコンウェハー基板上に、下記実施例及び比較例で得た樹脂組成物をスピンコートしたのち、ホットプレートを用いて90℃で2分間プリベークして、膜厚2.5μmの樹脂膜を形成した。次いで、0.4重量%テトラメチルアンモニウムヒドロキシド水溶液を用いて、25℃で60秒間現像処理を行ったのち、超純水で30秒間リンスした。そして、この樹脂膜に365nmにおける光強度が5mW/cm2である紫外線を、60秒間空気中で照射した。さらに、オーブンを用いて、230℃で60分間加熱することにより、ポストベークを行い、樹脂膜を有するシリコンウェハーを得た。そして、シリコンウェハー中央部の平坦な樹脂膜が得られた部分を、約1cm角、約1cm2の正方形状に裁断した。その後、温度25℃、湿度50%の雰囲気下に30分間放置することで、吸水性測定用試料を得た。
吸水性の測定は、次の方法により、行った。すなわち、上記にて得られた吸水性測定用試料を、昇温脱離ガス分析装置(略称TDS、電子科学株式会社製、型番「WA1000S/W」)を用いて、60℃/分で230℃まで昇温して、30分保持し、単位面積当たりに検出された水分量を吸水性の値とした。吸水性の値が低いほど、水を含み難く、水に対して高い絶縁性を有する良質な樹脂膜であるということが言える。
〔密着性測定用試料の作製〕
10cm角のガラス基板[コーニング社、コーニング1737(製品名)]上に、下記実施例及び比較例で得た樹脂組成物をスピンコートしたのち、ホットプレートを用いて90℃で2分間プリベークして、膜厚2.5μmの樹脂膜を形成した。次いで、光が透過する短冊状のスリット(スペースに相当)を平行して10本有し、該スリットの、1つのスリットとそのすぐ隣のスリットとの間(ラインに相当)の幅がスリット幅と同一であるマスクを介して、パターンが形成できる程度の所望の強度の光を所望の時間にて露光を行った。なお、本評価においては、スリット幅及び前記スリットの1つのスリットとそのすぐ隣のスリットとの間の幅が、それぞれ1μm、2μm、3μm、4μm、5μm、10μm、25μm及び50μmである8種のマスクを使用した試料を作製した。次いで、露光を行なった樹脂膜について、0.4重量%テトラメチルアンモニウムヒドロキシド水溶液を現像液として用いて、23℃で60秒間、パドル法により現像処理を行ったのち、超純水で30秒間リンスした。なお、パドル法とは、樹脂膜上に現像液を盛り静置する方法である。以上により、ガラス基板上に、マスクパターンが転写されたパターン(ラインアンドスペースのパターン)を有する樹脂膜を作製した。なお、下記実施例及び比較例で得た樹脂組成物は、ポジ型の感放射線能を有するものであり、そのため、前記樹脂膜においては、マスクのスリット部にあたる部分は樹脂膜が除去された部分にあたり、この部分をスペース部と呼ぶ。一方、マスクの1つのスリットとそのすぐ隣のスリットとの間にあたる部分は樹脂膜が残された部分にあたり、この部分をライン部と呼ぶ。そして、このようにして、得られたパターンを有する樹脂膜が形成されたガラス基板を密着性測定試料とした。
密着性の測定は、次の方法により、行った。すなわち、上記にて得られた密着性測定用試料を、光学顕微鏡を用いて観察し、ライン部における、基板からの剥がれの有無を確認することにより、密着性の測定を行なった。ライン部に剥がれが無ければ密着性が高いと言える。また、ライン部に剥がれが有った場合には、最大で何μm幅のライン部にまで剥がれが有るかを確認した。ライン部は幅が小さいほど基板から剥がれやすい。そのため、ライン部の基板からの剥がれが確認された場合には、剥がれが確認されたライン部の最大幅(剥がれが確認されたライン部のうち、幅が最大のものの幅の値)が小さいほど、密着性が高いと言える。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド100部、1,5-ヘキサジエン2部、(1,3-ジメシチルイミダゾリン-2-イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムクロリド(Org.Lett.,第1巻,953頁,1999年に記載された方法で合成した)0.02部、及びジエチレングリコールメチルエチルエーテル400部を、窒素置換したガラス製耐圧反応器に仕込み、攪拌しつつ80℃にて4時間反応させて重合体A1の重合反応液を得た。得られた重合体A1の重合転化率は99.6%、重量平均分子量は5,660、数平均分子量は3,510、分子量分布は1.49であった。
重合体A1のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。重合体A1は、25℃のMIBKに可溶であった。
実施例1で得た重合体A1の重合反応液をオートクレーブに入れて、150℃、水素圧4MPaで、5時間攪拌して水素化反応を行い、水素添加物A2を得た。得られた水素添加物A2の重量平均分子量は7,010、数平均分子量は4,590、分子量分布は1.53、水素添加率は、99.8%であった。
水素添加物A2のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A2は、25℃のMIBKに可溶であった。
特開2006-016606号公報に記載されている公知の方法によって、N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドの付加重合体A3を得た。付加重合体A3の重合転化率は78.3%、重量平均分子量は75,400、数平均分子量は36,200であった。
重合体A3のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。重合体A3は、25℃のMIBKに可溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドの代わりにN-(2-エチルヘキシル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドを用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A4を得た。得られた水素添加物A4の重合転化率は99.5%、重量平均分子量は7,140、数平均分子量は4,680、分子量分布は1.53、水素添加率は、99.8%であった。
水素添加物A4のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A4は、25℃のMIBKに可溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドの代わりにN-(1-メチルトリドデシル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドを用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A5を得た。得られた水素添加物A5の重合転化率は99.5%、重量平均分子量は7,250、数平均分子量は4,700、分子量分布は1.54、水素添加率は、99.7%であった。
水素添加物A5のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A5は、25℃のMIBKに可溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド100部の代わりにN-(2-エチルヘキシル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド80部、および8-ヒドロキシカルボニルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン20部を用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A6を得た。得られた水素添加物A6の重合転化率は99.6%、重量平均分子量は6,900、数平均分子量は4,570、分子量分布は1.51、水素添加率は、99.9%であった。
水素添加物A6のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A6は、25℃のMIBKに可溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド100部の代わりにN-(2-エチルヘキシル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド60部、および8-ヒドロキシカルボニルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン40部を用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A7を得た。得られた水素添加物A7の重合転化率は99.7%、重量平均分子量は6,780、数平均分子量は4,450、分子量分布は1.52、水素添加率は、99.9%であった。
水素添加物A7のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A7は、25℃のMIBKに可溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドの代わりにN-(tert-ブチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドを用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A8を得た。得られた水素添加物A8の重合転化率は99.6%、重量平均分子量は6,960、数平均分子量は4,400、分子量分布は1.58、水素添加率は、99.8%であった。
水素添加物A8のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A8は、25℃のMIBKに不溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミドの代わりにN-(エンド-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジイルジカルボニル)アスパラギン酸メチルを用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A9を得た。得られた水素添加物A9の重合転化率は99.8%、重量平均分子量は6,850、数平均分子量は4,490、分子量分布は1.53、水素添加率は、99.7%であった。
水素添加物A9のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A9は、25℃のMIBKに不溶であった。
N-(1-メチルペンチル)-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド100部の代わりにN-(エンド-ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジイルジカルボニル)アスパラギン酸メチル40部、および8-ヒドロキシカルボニルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン60部を用いた以外は、実施例1と同様にして、重合反応液を得て、得られた重合反応液を用いて、実施例2と同様にして、水素化反応を行うことにより、水素添加物A10を得た。得られた水素添加物A10の重合転化率は99.7%、重量平均分子量は6,950、数平均分子量は4,630、分子量分布は1.50、水素添加率は、99.7%であった。
水素添加物A10のメチルイソブチルケトン(MIBK)溶解性を評価した。評価結果を表1に示す。水素添加物A10は、25℃のMIBKに不溶であった。
重合体(A)として実施例6で得た水素添加物A6 100重量部、溶剤(B)としてジエチレングリコールエチルメチルエーテル(EDM)550重量部、架橋剤(C)としてエポキシ化ブタンテトラカルボン酸テトラキス(3-シクロヘキセニルメチル)修飾ε-カプロラクトン(脂環族環状4官能性のエポキシ樹脂、商品名「エポリードGT401」、ダイセル化学工業社製)50重量部、界面活性剤としてシリコーン系界面活性剤(信越化学工業社製、「KP-341(製品名)」)0.05重量部を混合し溶解させた後、孔径0.45μmのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物1を調製した。
この樹脂組成物1を用いて、吸水性を評価した。結果を表2に示す。
水素添加物A6の代わりに、それぞれ、水素添加物A7(実施例9)、水素添加物A9(比較例4)、水素添加物A10(比較例5)を用いた以外は、実施例8と同様にして樹脂組成物2~4を調製した。
これらの樹脂組成物2~4を用いて、吸水性を評価した。結果を表2に示す。
重合体(A)として実施例6で得た水素添加物A6 100重量部、溶剤(B)としてジエチレングリコールエチルメチルエーテル(EDM)550重量部、感放射線化合物(D)である1,2-キノンジアジド化合物として1,1,3-トリス(2,5-ジメチル-4-ヒドロキシフェニル)-3-フェニルプロパン(1モル)と1,2-ナフトキノンジアジド-5-スルホン酸クロリド(1.9モル)との縮合物30重量部、界面活性剤としてシリコーン系界面活性剤(信越化学工業社製、「KP-341(製品名)」)0.05重量部を混合し溶解させた後、孔径0.45μmのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物5を調製した。
この樹脂組成物5を用いて、密着性を評価した。結果を表3に示す。
水素添加物A6の代わりに、それぞれ、水素添加物A7(実施例11)、水素添加物A9(比較例6)、水素添加物A10(比較例7)を用いた以外は、実施例10と同様にして樹脂組成物6~8を調製した。
これらの樹脂組成物6~8を用いて、密着性を評価した。結果を表3に示す。
Claims (11)
- 前記一般式(1)で表される単量体と、該単量体と共重合可能な単量体とを共重合してなる請求項1に記載の重合体。
- 前記共重合可能な単量体が、プロトン性極性基を有する環状オレフィン単量体である請求項2に記載の重合体。
- 前記プロトン性極性基を有する環状オレフィン単量体が、カルボキシル基含有環状オレフィン単量体である請求項3に記載の重合体。
- 開環重合体である請求項1~4のいずれかに記載の重合体。
- 請求項5に記載の開環重合体の水素添加物。
- 重合体(A)及び溶剤(B)を含有する樹脂組成物であって、
前記重合体(A)が、請求項1~5のいずれかに記載の重合体及び/又は請求項6に記載の開環重合体の水素添加物であることを特徴とする樹脂組成物。 - 前記樹脂組成物が、さらに架橋剤(C)を含有するものである請求項7に記載の樹脂組成物。
- 前記樹脂組成物が、さらに感放射線化合物(D)を含有するものである請求項7又は8に記載の樹脂組成物。
- 請求項7~9のいずれかに記載の樹脂組成物を用いて形成される樹脂膜。
- 請求項10に記載の樹脂膜を有する電子部品。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011506090A JP5561271B2 (ja) | 2009-03-26 | 2010-03-24 | 樹脂組成物、樹脂膜及び電子部品 |
KR1020117025042A KR101706796B1 (ko) | 2009-03-26 | 2010-03-24 | 중합체, 수소 첨가물, 수지 조성물, 수지막 및 전자 부품 |
CN201080013512.1A CN102365303B (zh) | 2009-03-26 | 2010-03-24 | 聚合物、聚合物的氢化物、树脂组合物、树脂膜及电子部件 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009075333 | 2009-03-26 | ||
JP2009-075333 | 2009-03-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010110323A1 true WO2010110323A1 (ja) | 2010-09-30 |
Family
ID=42781016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/055095 WO2010110323A1 (ja) | 2009-03-26 | 2010-03-24 | 重合体、水素添加物、樹脂組成物、樹脂膜及び電子部品 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5561271B2 (ja) |
KR (1) | KR101706796B1 (ja) |
CN (1) | CN102365303B (ja) |
TW (1) | TWI494345B (ja) |
WO (1) | WO2010110323A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012171994A (ja) * | 2011-02-18 | 2012-09-10 | Nippon Zeon Co Ltd | 樹脂組成物および半導体素子基板 |
CN102707570A (zh) * | 2011-03-21 | 2012-10-03 | 奇美实业股份有限公司 | 感光性树脂组成物、间隙体及含彼的液晶显示元件 |
WO2017163981A1 (ja) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | 樹脂組成物、樹脂膜、及び電子部品 |
JPWO2016133023A1 (ja) * | 2015-02-19 | 2017-11-30 | 日本ゼオン株式会社 | 樹脂組成物、樹脂膜、及び電子部品 |
EP2826802B1 (en) * | 2012-03-16 | 2021-03-10 | Zeon Corporation | Method for producing ring-opening metathesis polymer hydride, and resin composition |
US11169440B2 (en) | 2017-03-30 | 2021-11-09 | Zeon Corporation | Radiation-sensitive resin composition and electronic component |
WO2021241516A1 (ja) | 2020-05-29 | 2021-12-02 | 日本ゼオン株式会社 | マイクロ流路チップ及びその製造方法 |
WO2021241517A1 (ja) | 2020-05-29 | 2021-12-02 | 日本ゼオン株式会社 | 接合体及びその製造方法 |
WO2022255150A1 (ja) | 2021-05-31 | 2022-12-08 | 日本ゼオン株式会社 | 樹脂組成物および光学素子 |
WO2023053952A1 (ja) | 2021-09-30 | 2023-04-06 | 日本ゼオン株式会社 | 積層体及びその製造方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10025182B2 (en) * | 2014-03-20 | 2018-07-17 | Zeon Corporation | Radiation-sensitive resin composition and electronic device |
WO2018101204A1 (ja) * | 2016-11-30 | 2018-06-07 | 日本ゼオン株式会社 | 偏光板、及び、偏光板の製造方法 |
CN111032788B (zh) * | 2017-09-28 | 2022-03-08 | 日本瑞翁株式会社 | 树脂组合物及树脂膜 |
CN110317321B (zh) * | 2019-06-28 | 2020-09-01 | 东莞理工学院 | 一种醌式共轭聚合物及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1594934A (ja) * | 1968-12-05 | 1970-06-08 | ||
KR20100009996A (ko) * | 2008-07-21 | 2010-01-29 | 동우 화인켐 주식회사 | 적색 감광성 수지 조성물, 컬러필터 및 이를 구비한액정표시장치 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0778115B2 (ja) * | 1987-04-16 | 1995-08-23 | 帝人株式会社 | 架橋重合体成型物の製造方法および反応性溶液の組合せ |
US5115037A (en) | 1990-12-19 | 1992-05-19 | Monsanto Company | Hydrogenated cyclic alkyl polymers |
KR100493015B1 (ko) * | 2001-08-25 | 2005-06-07 | 삼성전자주식회사 | 감광성 폴리머 및 이를 포함하는 포토레지스트 조성물 |
JP2003301032A (ja) | 2002-04-11 | 2003-10-21 | Nippon Zeon Co Ltd | ノルボルネン系開環重合体、ノルボルネン系開環重合体水素化物およびそれらの製造方法 |
JP2008156569A (ja) * | 2006-12-26 | 2008-07-10 | Nippon Zeon Co Ltd | ノルボルネン化合物重合体水素添加物の精製方法、これにより得られるノルボルネン化合物重合体水素添加物、これからなる成形材料及びその成形体 |
JP2008222935A (ja) | 2007-03-14 | 2008-09-25 | Nippon Zeon Co Ltd | 重合体およびその水添物 |
JP7078115B2 (ja) | 2018-07-26 | 2022-05-31 | 株式会社島津製作所 | 光散乱検出装置 |
-
2010
- 2010-03-24 CN CN201080013512.1A patent/CN102365303B/zh active Active
- 2010-03-24 JP JP2011506090A patent/JP5561271B2/ja active Active
- 2010-03-24 KR KR1020117025042A patent/KR101706796B1/ko active IP Right Grant
- 2010-03-24 WO PCT/JP2010/055095 patent/WO2010110323A1/ja active Application Filing
- 2010-03-25 TW TW099108865A patent/TWI494345B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1594934A (ja) * | 1968-12-05 | 1970-06-08 | ||
KR20100009996A (ko) * | 2008-07-21 | 2010-01-29 | 동우 화인켐 주식회사 | 적색 감광성 수지 조성물, 컬러필터 및 이를 구비한액정표시장치 |
Non-Patent Citations (1)
Title |
---|
C. T. VIJAYAKUMAR ET AL.: "Structural aspects of polyimides. I. Polymerization and degradation of endo-N- phenylnadimide and endo-N-isobutylnadimide", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, vol. 27, no. 8, 1989, pages 2723 - 2748 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012171994A (ja) * | 2011-02-18 | 2012-09-10 | Nippon Zeon Co Ltd | 樹脂組成物および半導体素子基板 |
CN102707570A (zh) * | 2011-03-21 | 2012-10-03 | 奇美实业股份有限公司 | 感光性树脂组成物、间隙体及含彼的液晶显示元件 |
CN102707570B (zh) * | 2011-03-21 | 2014-08-06 | 奇美实业股份有限公司 | 感光性树脂组成物、间隙体及含彼的液晶显示元件 |
EP2826802B1 (en) * | 2012-03-16 | 2021-03-10 | Zeon Corporation | Method for producing ring-opening metathesis polymer hydride, and resin composition |
JPWO2016133023A1 (ja) * | 2015-02-19 | 2017-11-30 | 日本ゼオン株式会社 | 樹脂組成物、樹脂膜、及び電子部品 |
WO2017163981A1 (ja) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | 樹脂組成物、樹脂膜、及び電子部品 |
US11169440B2 (en) | 2017-03-30 | 2021-11-09 | Zeon Corporation | Radiation-sensitive resin composition and electronic component |
WO2021241516A1 (ja) | 2020-05-29 | 2021-12-02 | 日本ゼオン株式会社 | マイクロ流路チップ及びその製造方法 |
WO2021241517A1 (ja) | 2020-05-29 | 2021-12-02 | 日本ゼオン株式会社 | 接合体及びその製造方法 |
WO2022255150A1 (ja) | 2021-05-31 | 2022-12-08 | 日本ゼオン株式会社 | 樹脂組成物および光学素子 |
WO2023053952A1 (ja) | 2021-09-30 | 2023-04-06 | 日本ゼオン株式会社 | 積層体及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2010110323A1 (ja) | 2012-10-04 |
JP5561271B2 (ja) | 2014-07-30 |
KR101706796B1 (ko) | 2017-02-14 |
CN102365303B (zh) | 2014-02-26 |
CN102365303A (zh) | 2012-02-29 |
KR20120001779A (ko) | 2012-01-04 |
TWI494345B (zh) | 2015-08-01 |
TW201038617A (en) | 2010-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5561271B2 (ja) | 樹脂組成物、樹脂膜及び電子部品 | |
JP5488460B2 (ja) | 感放射線樹脂組成物、積層体及びその製造方法ならびに半導体デバイス | |
JP6947027B2 (ja) | 樹脂組成物、樹脂膜、及び電子部品 | |
JPWO2012165448A1 (ja) | 樹脂組成物および半導体素子基板 | |
JP5522176B2 (ja) | 半導体素子基板 | |
JP5747908B2 (ja) | 半導体素子基板の製造方法 | |
JPWO2012133617A1 (ja) | 樹脂組成物および半導体素子基板 | |
JP5640864B2 (ja) | ネガ型感光性樹脂組成物および電子部品 | |
JP5589286B2 (ja) | 薄膜トランジスタの製造方法、及び薄膜トランジスタ並びに表示装置 | |
JP5413097B2 (ja) | 感放射線性樹脂組成物、及び積層体 | |
JP6248561B2 (ja) | 感放射線性樹脂組成物、及び積層体 | |
JP2011075610A (ja) | 感放射線性樹脂組成物、及び積層体 | |
JP6183029B2 (ja) | ネガ型感光性樹脂組成物および電子部品 | |
JP2012049300A (ja) | 半導体素子基板 | |
JP2012171993A (ja) | 樹脂組成物および半導体素子基板 | |
JP2011105688A (ja) | 単量体の精製方法 | |
JP2012171994A (ja) | 樹脂組成物および半導体素子基板 | |
JP2010072217A (ja) | 感放射線樹脂組成物、樹脂膜及び電子部品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080013512.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10756119 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011506090 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117025042 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10756119 Country of ref document: EP Kind code of ref document: A1 |