WO2012132150A1 - Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin resin film - Google Patents
Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin resin film Download PDFInfo
- Publication number
- WO2012132150A1 WO2012132150A1 PCT/JP2011/079945 JP2011079945W WO2012132150A1 WO 2012132150 A1 WO2012132150 A1 WO 2012132150A1 JP 2011079945 W JP2011079945 W JP 2011079945W WO 2012132150 A1 WO2012132150 A1 WO 2012132150A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cyclic olefin
- thermosetting crosslinked
- olefin resin
- ring
- crosslinked cyclic
- Prior art date
Links
- POKQCCVKEUHHGT-UHFFFAOYSA-N CC(N(CC1)SC)N1SC Chemical compound CC(N(CC1)SC)N1SC POKQCCVKEUHHGT-UHFFFAOYSA-N 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
Definitions
- the present invention relates to a thermosetting crosslinked cyclic olefin resin composition having a large water contact angle on the surface and a thermosetting crosslinked cyclic olefin resin film comprising the composition.
- the film made of the resin composition according to the present invention is used in a mounting process such as a semiconductor sealing process such as an IC chip or an LED, a laminated heat pressing process when manufacturing a multilayer printed wiring board, or a coverlay attaching process when manufacturing a flexible printed wiring board. Contributes to yield improvement.
- this invention relates to the manufacturing method of the said composition, and the manufacturing method of the said film.
- Olefin resin is mainly used as a raw material for various molded products.
- One of the uses of a molded product using an olefin resin is a resin film. Widely used because of its advantages such as transparency, light weight, good processability, and easy incineration. However, there is a drawback in that the heat resistance is poor, and it cannot be used in applications where the temperature is 100 ° C. or higher.
- a release film in a semiconductor manufacturing process is a use of a resin film having high temperature and heat resistance.
- a mold release film is a film used for mold release with a sealing material, a prepreg, or the like in a semiconductor element sealing process.
- the downsizing and thinning of semiconductor elements such as IC chips and LEDs are progressing along with the downsizing and thinning of mobile devices such as mobile phones.
- the shape of the sealing chip that seals these elements has also changed. Recently, a chip with a shape in which a lead frame is arranged so as to extend from a sealing chip as seen in a conventional surface mounting element is not mainstream, and a chip size that is a shape in which terminals are arranged directly on the element.
- Mounting sealing chips in the form of packages (CSP), ball grid arrays (BGA), quad flat now lead packages (QFN) and the like are becoming mainstream. These shapes have the advantage of a small mounting area and contribute to the downsizing of the equipment. Furthermore, the sealing chip for mounting in these shapes is thin, which contributes to a reduction in the sealing film thickness.
- a cross-linked resin film obtained by polymerizing a liquid containing a metathesis polymerization catalyst and a cycloolefin capable of metathesis polymerization on a carrier was studied as a release film (see, for example, Patent Document 3).
- the film has a small water contact angle and does not have sufficient releasability from the resin used for the sealing material, prepreg, and adhesive.
- thermosetting crosslinked cyclic olefin resins obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, the sealing material, prepreg, and releasability before and after sufficient heating of the resin used in the adhesive, the tensile elongation at break, and mechanical strength such as tensile strength, has a water-repellent, high temperature discoloration resistance, a resin composition which gives a film that can be burned at the time of disposal has been desired, seen such a resin composition It was not put out.
- An object of the present invention is to provide, include thermosetting crosslinked cyclic olefin resins obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, the sealing material, prepreg, sufficient heating of the resin used in the adhesive and the release of the front and rear, tensile elongation at break, and mechanical strength such as tensile strength, and water-repellent resin composition which gives a film having a high temperature discoloration resistance, film comprising the resin composition, of the composition It is provision of the manufacturing method and the manufacturing method of the said film.
- the inventor of the present invention has (a) a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds] and (c) for 1 minute.
- a thermosetting crosslinked cyclic olefin resin composition obtained by heating a polymerizable composition containing an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. to perform ring-opening metathesis polymerization and crosslinking is sealed.
- the present invention has been found to provide a film having sufficient releasability before and after heating, high mechanical strength, high water repellency, and high temperature discoloration resistance with a resin used for a stopper, prepreg, and adhesive.
- the present invention has been completed with a conductive crosslinked cyclic olefin resin composition, a film comprising the resin composition, and a method for producing them.
- thermosetting crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds].
- the composition is obtained by heating and ring-opening metathesis polymerization and crosslinking.
- thermosetting crosslinked cyclic olefin resin film of the present invention comprises the above composition.
- the preferable use of the said thermosetting crosslinked cyclic olefin resin film is a release film used for a semiconductor sealing process or a printed circuit board manufacturing process.
- thermosetting crosslinked cyclic olefin resin composition of the present invention is (a) 100 parts by mass of a cyclic olefin monomer, (b) [other than the above (a), and has two or more polymerizable unsaturated bonds. Agent] 0.7 to 40 parts by mass and (c) 1.15 to 15 parts by mass of an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute and (d) a ring-opening metathesis polymerization catalyst Heating the polymerizable composition to perform ring-opening metathesis polymerization and crosslinking.
- the method for producing the thermosetting crosslinked cyclic olefin resin film of the present invention includes (a) 100 parts by mass of a cyclic olefin monomer, (b) [other than (a), and a crosslinking agent having two or more polymerizable unsaturated bonds. ] 0.7-40 parts by mass and (c) 1.15-15 parts by mass of an organic peroxide thermal polymerization initiator having a half-life temperature of 135-200 ° C. for 1 minute and (d) a ring-opening metathesis polymerization catalyst
- the method includes applying the polymerizable composition on a support and heating to perform ring-opening metathesis polymerization and crosslinking on the support.
- Thermosetting crosslinked cyclic olefin resin composition of the present invention the sealing material, prepreg, and releasability before and after sufficient heating of the resin used in the adhesive, tensile elongation at break, mechanical such as tensile strength at break A film having strength, water repellency, and high temperature discoloration resistance is provided.
- the cyclic olefin monomer (a) which is one of the raw materials of the thermosetting crosslinked cyclic olefin resin composition of the present invention has a ring structure formed of carbon atoms, and a carbon-carbon double bond is formed in the ring. It is a compound that has. Specific examples thereof include norbornene monomers and monocyclic olefins.
- the preferred (a) cyclic olefin monomer is a norbornene monomer.
- the norbornene-based monomer is a monomer containing a norbornene ring. Specific examples of the norbornene monomer include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain as substituents hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups; polar groups such as carboxyl groups and acid anhydride groups.
- the norbornene-based monomer may further have a double bond in addition to the double bond of the norbornene ring.
- a preferred norbornene-based monomer is a non-polar norbornene-based monomer composed of only carbon atoms and hydrogen atoms.
- nonpolar norbornene-based monomer examples include nonpolar such as dicyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.02,6] dec-8-ene).
- pentadeca -4,6,8,13- tetraene (. 1,4-methano -1,4,4a, 9, 9a, also referred to as 10-hexa hydro anthracene) nonpolar norbornene, such as; Pentacyclo [6.5.1.13, 6.02, 7.09, 13] pentadeca-4,10-diene, pentacyclo [9.2.14, 7.02, 10.03,8] pentadeca
- Non-polar cyclic olefins having five or more rings such as 5,12-diene, hexacyclo [6.6.1.13, 6.110, 13.02, 7.09,14] heptade-4-ene; It is.
- non-polar norbornene-type monomer a non-polar di- cyclopentadienes, nonpolar tetracyclododecene compound, more preferably a non-polar norbornene-type monomer, a non-polar di Cyclopentadiene.
- norbornene-based monomer containing a polar group examples include tetracyclo [6.2.13, 6.02,7] dodec-9-ene-4-carboxylate, tetracyclo [6.2.1.13, 6.02,7] dodec-9-ene-4-methanol, tetracyclo [6.2.13,6.02,7] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1 .13,6.02,7] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.13,6.02,7] dodec-9-ene-4,5-dicarboxylic acid Anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, 5-norbornene-2-methanol, 5-norbornene-2- All, 5-norbol Down 2-carbonitrile
- monocyclic olefin examples include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent.
- the addition amount of the monocyclic olefin is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the (a) cyclic olefin monomer.
- the addition amount of the monocyclic cyclic olefin is 40% by mass or less, the heat resistance of the obtained thermosetting crosslinked cyclic olefin resin composition and the thermosetting crosslinked cyclic olefin resin film is sufficient.
- A a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds], (c) an organic peroxide having a half-temperature of 135 to 200 ° C. for 1 minute
- the polymerizable composition containing the system thermal polymerization initiator and (d) the ring-opening metathesis polymerization catalyst is heated to undergo ring-opening metathesis polymerization and crosslinking.
- the ring-opening metathesis polymerization catalyst (a) causes ring-opening metathesis polymerization of a cyclic olefin monomer.
- the polymerization catalyst is not limited to a specific catalyst.
- a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom is used as (d) a ring-opening metathesis polymerization catalyst.
- Atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same applies hereinafter) are used as transition metal atoms.
- preferred Group 5 atoms is tantalum
- a tungsten atom of the preferred group 8 is ruthenium or osmium.
- Preferred (d) ring-opening metathesis polymerization catalyst, Group 8 ruthenium, a complex of osmium, particularly preferably (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, a crosslinked cyclic olefin polymer with little residual unreacted monomer can be obtained with high productivity.
- a specific example of the ruthenium carbene complex is a complex represented by the following formula (1) or (2) from the viewpoint of catalytic activity.
- R 1 and R 2 each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms.
- X 1 and X 2 each independently represent an arbitrary anionic ligand.
- L 1 and L 2 each independently represents a neutral electron donating compound.
- R 1 and R 2 may be bonded to each other to contain a hetero atom, and may form an aliphatic ring or an aromatic ring.
- R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be bonded together in any combination to form a multidentate chelating ligand.
- the heteroatom in the present invention is an atom of Groups 15 and 16 of the periodic table.
- Specific examples of the hetero atom include a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), and a selenium atom (Se).
- preferred heteroatoms are N, O, P, and S, and particularly preferred heteroatoms are N.
- Neutral electron donating compounds are roughly classified into heteroatom-containing carbene compounds and other neutral electron donating compounds.
- preferred neutral electron donating compounds are heteroatom-containing carbene compounds.
- a heteroatom-containing carbene compound in which heteroatoms are bonded adjacent to each other on both sides of the carbene carbon is preferable, and a heteroatom-containing carbene compound in which a heterocycle is formed including the carbene carbon atom and the heteroatoms on both sides thereof is more preferable.
- the heteroatom adjacent to the carbene carbon preferably has a bulky substituent.
- preferable heteroatom-containing carbene compounds are compounds represented by the following formula (3) or formula (4).
- R 3 to R 6 may each independently contain a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R 3 to R 6 may be bonded to each other in any combination to form a ring.
- formula (3) or the compound represented by formula (4) is 1,3-mesityl imidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene 1-cyclohexyl-3-mesitylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3- And di (1-phenylethyl) -4-imidazoline-2-ylidene and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene.
- the neutral electron donating compound other than the heteroatom-containing carbene compound is a ligand having a neutral charge when pulled away from the central metal.
- Specific examples of the neutral electron donating compound include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. is there.
- Preferred neutral electron donating compounds are phosphines, ethers and pyridines, and a more preferred neutral electron donating compound is trialkylphosphine.
- the anionic (anionic) ligands X 1 and X 2 are ligands having a negative charge when separated from the central metal atom.
- halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, carboxyl group Etc.
- a preferred anionic ligand is a halogen atom, and a more preferred ligand is a chlorine atom.
- Z represents an oxygen atom, a sulfur atom, a selenium atom, NR 12 , PR 12 or AsR 12 , and R 12 is the same as those exemplified for R 1 and R 2 .
- R 7 to R 9 each independently represents a monovalent organic group which may contain a hydrogen atom, a halogen atom, or a hetero atom.
- the monovalent organic group which may contain a hetero atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, An alkoxyl group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms
- the monovalent organic group that may contain these heteroatoms may have a substituent and may be bonded to each other to form a ring.
- substituents are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group.
- the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.
- R 10 and R 11 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group, and these groups are May have a substituent and may be bonded to each other to form a ring.
- substituents are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group.
- the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.
- complex compound represented by the formula (1) examples include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4).
- Mes represents a mesityl group.
- R 7 and R 8 are each a hydrogen atom or a methyl group, and at least one of them is a methyl group.
- R 13 and R 14 each independently represents a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom.
- the “monovalent organic group” is the same as R 7 to R 9 described above in the description of the formula (5).
- the complex compound represented by the formula (2) include (1,3-dimesityl-4-imidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (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 most preferable complex compound has one compound represented by the formula (1) and represented by the formula (3) or (4) as a ligand.
- the amount of the (d) ring-opening metathesis polymerization catalyst used is usually 1: 2,000 to 1: 2, in a molar ratio of ((d) metal atom in the ring-opening metathesis polymerization catalyst: (a) cyclic olefin monomer).
- the range is from 1,000,000, preferably from 1: 5,000 to 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000.
- D When the molar ratio of the amount of the ring-opening metathesis polymerization catalyst to the (a) cyclic olefin monomer is 1 / 2,000,000 or more, a sufficient polymerization reaction rate is obtained, and the monomer remains in the polymer.
- thermosetting cross-linked cyclic olefin resin composition and thermosetting cross-linked cyclic olefin resin film can be prevented from decreasing.
- D By making the molar ratio of the amount of the ring-opening metathesis polymerization catalyst to (a) the cyclic olefin monomer 1/2000 or less, the production cost can be reduced, and the reaction rate is prevented from becoming too fast. The molding of a thermosetting crosslinked cyclic olefin resin film at the time of bulk polymerization described later is facilitated.
- the ring-opening metathesis polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate.
- an activator include aluminum, scandium, tin, silicon alkylates, halides, alkoxylates and aryloxylates.
- activators include aluminum compounds such as trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride; trialkoxy Scandium compounds such as scandium; titanium compounds such as tetraalkoxy titanium; tin compounds such as tetraalkyls and tetraalkoxytin; zirconium compounds such as tetraalkoxyzirconium; dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, bicyclo Heptenylmethyldichlorosilane, phenylmethyldichlorosilane, Hexyl dichlorosilane, phenyl trichlorosilane, silane compounds such as trialk
- the use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1 in terms of a molar ratio of ((d) metal atom in ring-opening metathesis polymerization catalyst: activator). : 20, more preferably in the range of 1: 0.5 to 1:10.
- the ring-opening metathesis polymerization catalyst can be used in combination with a polymerization regulator for the purpose of controlling the polymerization activity and adjusting the polymerization reaction rate.
- a polymerization regulator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,1-bis (diphenylphosphino) methane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenyl).
- Phosphino) phosphorus compounds such as pentane
- Lewis bases such as ethers, esters and nitriles.
- the amount of these used is usually 0.01 to 50 mol, preferably 0.05 to 10 mol, relative to 1 mol of (d) the ring-opening metathesis polymerization catalyst.
- Either the solution polymerization method or the bulk polymerization method may be applied to the method for producing the thermosetting crosslinked cyclic olefin resin composition and the thermosetting crosslinked cyclic olefin resin film of the present invention, but no solvent removal step is required. From the viewpoint that a resin composition molded into a film shape at the same time as polymerization can be obtained, it is preferable to apply a bulk polymerization method.
- the method for producing the thermosetting crosslinked cyclic olefin resin composition of the present invention includes (a) a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds] and (C) a polymerizable composition containing an organic peroxide thermal polymerization initiator having a half-life temperature of 135 to 200 ° C. for 1 minute and (d) a ring-opening metathesis polymerization catalyst, in the presence of an additive used as necessary. And a ring-opening metathesis polymerization and crosslinking step.
- thermosetting crosslinked cyclic olefin resin film of this invention is (a) Cyclic olefin monomer, (b) [Other than said (a), and the crosslinking agent which has two or more polymerizable unsaturated bonds] And (c) the presence of an additive that is used as necessary for a polymerizable composition containing an organic peroxide thermal polymerization initiator having a half-life temperature of 135 to 200 ° C. for 1 minute and (d) a ring-opening metathesis polymerization catalyst. It includes a step of heating down to form a film by ring-opening metathesis polymerization and crosslinking.
- the cyclic olefin monomer is subjected to ring-opening metathesis polymerization to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the ring-opening metathesis polymerization or simultaneously with the ring-opening metathesis polymerization. It is believed that a polymer is obtained.
- the three-dimensional crosslinked structure of the cyclic olefin polymer, the thermosetting crosslinked cyclic olefin resin composition and the thermosetting crosslinked cyclic olefin resin film is confirmed by the solubility in 1,2-dichlorobenzene.
- the cyclic olefin polymer was immersed for 24 hours at 23 ° C. in 1,2-dichlorobenzene, a polymer insoluble component mass when the resulting solution was filtered through a 80-mesh metal gauze and before the original filtration polymer
- the degree of crosslinking obtained by dividing by the mass of is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more. By being 70 mass% or more, better heat resistance and mechanical strength can be obtained, and contamination of the substrate, mold, press device, etc. due to uncrosslinked components can be suppressed.
- the polymerizable composition which is a raw material of the thermosetting crosslinked cyclic olefin resin composition of the present invention contains (b) a crosslinking agent having two or more polymerizable unsaturated bonds.
- crosslinking agents include pentaerythritol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane Two or more polymerizations such as tri (meth) acrylate, pentaerythritol tri (meth)
- a crosslinking agent having one or two or more polymerizable unsaturated bonds is used.
- the content of (b) [other than (a) and a crosslinking agent having two or more polymerizable unsaturated bonds] is 0.7 to 40 parts by mass with respect to 100 parts by mass of (a) cyclic olefin monomer, The amount is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 4 to 10 parts by mass.
- the polymerizable composition as a raw material of the thermosetting crosslinked cyclic olefin resin composition of the present invention contains (c) an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute.
- an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute.
- Specific examples of the thermal polymerization initiator include 1,6-bis (t-butylperoxycarbonyloxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene.
- One or two or more organic peroxide thermal polymerization initiators having a half-temperature of 135 to 200 ° C. for 1 minute are used.
- the content of the organic peroxide thermal polymerization initiator having a half-life temperature of 135 to 200 ° C. per minute is 1.15 to 15 parts by mass, preferably 1 with respect to 100 parts by mass of the (a) cyclic olefin monomer. 5 to 10 parts by mass, more preferably 2 to 8 parts by mass.
- (C) If the content of the organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute is too small, the mold release property before and after heating of the thermosetting crosslinked cyclic olefin resin film, mechanical strength, The water repellency and high-temperature discoloration resistance are lowered, and the polymerizable composition may not be polymerized. On the other hand, if the content of (c) the organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute is too large, the polymerizable composition may not be polymerized.
- Polymerization that is a raw material for the thermosetting crosslinked cyclic olefin resin composition of the present invention, with various additives, for the purpose of various properties, film property modification, function addition, and improvement of molding workability according to purposes. Contained in the composition.
- additives include antioxidants, fillers, antifoaming agents, foaming agents, colorants, UV absorbers, light stabilizers, flame retardants, wetting agents, dispersants, mold release lubricants, plasticizers.
- Agents Preferably, an antioxidant and a light stabilizer are contained in order to improve the durability and storage stability of the crosslinked cyclic olefin polymer.
- antioxidants include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; di-t-butyl para Phenols such as cresol, hydroquinone monomethyl ether and pyrogallol; copper salts such as copper naphthenate and copper octenoate; quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride; quinonedioxime And oximes such as methyl ethyl ketoxime; amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride.
- antioxidants are appropriately selected depending on conditions such as mechanical properties at high temperature, film forming workability, and storage stability of the crosslinked cyclic olefin polymer. Phenols are preferred because they have high compatibility with the crosslinked cyclic olefin polymer, are uniformly dispersed, and improve the durability and storage stability of the film.
- One or more antioxidants are used in combination. The amount of the antioxidant used is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer.
- light stabilizers include hindered amine light stabilizer (HALS) compounds.
- HALS hindered amine light stabilizer
- Specific examples of hindered amine light stabilizer compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl- 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy -2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6 Pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl- ⁇ (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 1
- the kind and amount of these hindered amine light stabilizer compounds are appropriately selected depending on conditions such as mechanical properties at high temperature and storage stability of the crosslinked cyclic olefin polymer.
- One or more antioxidants are used in combination.
- the amount of the hindered amine light stabilizer compound used is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer.
- the filler include inorganic fillers such as silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic fillers such as wood powder, polyester beads, and polystyrene beads.
- the filler improves physical properties such as shrinkage rate, elastic modulus, thermal conductivity, and conductivity of the crosslinked cyclic olefin polymer.
- Grades such as particle size, shape, aspect ratio, and quality of the filler are appropriately determined depending on the physical properties of the crosslinked cyclic olefin polymer.
- the amount of these fillers to be used is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer.
- the release lubricant examples include silicone oil and zinc stearate.
- the mold release lubricant improves the moldability, mold release and handling properties of the film and imparts functions such as lubricant properties to the film.
- the amount of the release lubricant used is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer.
- A a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds], (c) an organic peroxide having a half-temperature of 135 to 200 ° C. for 1 minute
- a polymerizable composition containing a system thermal polymerization initiator and (d) a ring-opening metathesis polymerization catalyst is heated in the presence of an additive used as necessary to perform ring-opening metathesis polymerization and crosslinking.
- the ring-opening metathesis polymerization catalyst is used, if necessary, dissolved or suspended in a small amount of an inert solvent.
- the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl,
- Preferred solvents are aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.
- a liquid anti-aging agent or plasticizer that does not decrease the activity as a ring-opening metathesis polymerization catalyst may be used as a solvent.
- the viscosity at room temperature of the polymerizable composition containing a system thermal polymerization initiator, (d) a ring-opening metathesis polymerization catalyst and an additive used as necessary depends on the desired film thickness, but is usually 3 to 30, 000 Pa ⁇ s, preferably 5 to 500 Pa ⁇ s.
- the viscosity of the above composition is (a) a cyclic olefin monomer, (b) [a cross-linking agent other than the above (a) and having two or more polymerizable unsaturated bonds], (c) a 1 minute half-temperature of 135 to It is adjusted according to the type and amount of the organic peroxide thermal polymerization initiator at 200 ° C. and (d) the ring-opening metathesis polymerization catalyst.
- thermosetting crosslinked cyclic olefin resin composition of the present invention can be produced by heating the above polymerizable composition to bulk polymerization and crosslinking.
- Specific examples of the method for producing the thermosetting crosslinked cyclic olefin resin film of the present invention include a method of pouring or coating the polymerizable composition on a support, heating and bulk polymerization and crosslinking, and the polymerizable composition.
- the product is heated in a mold to perform bulk polymerization and crosslinking.
- the method of pouring or applying the polymerizable composition on a support and heating to perform bulk polymerization and crosslinking is more preferable because a thin and uniform film can be continuously produced.
- Specific known materials such as resin, glass and metal are selected as the support.
- the resin include polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyarylate; polyolefins such as polypropylene and polyethylene; polyamides such as nylon; fluororesins such as polytetrafluoroethylene; Is preferred.
- a preferable shape of the support is a drum or a belt if the material is metal or resin.
- a preferred support is a resin film that is easily available and inexpensive.
- the method for applying the polymerizable composition to the support is not particularly limited. Specific examples of the method include spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.
- the polymerizable composition is heated (d) to a temperature at which the ring-opening metathesis polymerization catalyst exhibits activity to perform bulk polymerization and crosslinking.
- the temperature for polymerization and crosslinking is usually 0 to 250 ° C., preferably 20 to 200 ° C.
- the method for heating the polymerizable composition is not particularly limited. Specific examples of the heating method include a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, a method of pressing with a heated roller, and a method of using a heating furnace.
- the reaction time for the polymerization and crosslinking is appropriately determined depending on the amount of the polymerization catalyst, the addition amount of the organic peroxide thermal polymerization initiator, the heating temperature, etc., but is usually 1 minute to 24 hours.
- the polymerizable composition is heated, and (b) [a cross-linking agent other than the above (a) and having two or more polymerizable unsaturated bonds] is (c) an organic having a half-temperature of 135 to 200 ° C. for 1 minute.
- Crosslinking reaction is performed with a peroxide thermal polymerization initiator. The crosslinking reaction is performed after the ring-opening metathesis polymerization or simultaneously with the ring-opening metathesis polymerization.
- the crosslinking reaction temperature is the temperature at which the ring-opening metathesis polymerization catalyst exhibits activity, (d) the addition amount of the ring-opening metathesis polymerization catalyst, the temperature at which the organic peroxide thermal polymerization initiator exhibits activity, the organic peroxide system It needs to be set in relation to the amount of the thermal polymerization initiator added, and is usually 130 to 250 ° C., preferably 150 to 230 ° C.
- the heating time is not particularly limited, but is usually from several minutes to several hours.
- the heating method for the polymerizable composition is not particularly limited. Specific examples of the heating method include a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, a method of pressing with a heated roller, and a method of using a heating furnace.
- A generation of radicals such as known diazo compounds and nonpolar radical generators
- B A method in which a known photopolymerization initiator is added to the composition and irradiated with light or an electron beam to cause polymerization and crosslinking reaction, and the like. You may use together with the method of adding and heating a system thermal polymerization initiator.
- the cyclic olefin polymer is also crosslinked by a crosslinkable cyclic olefin olefin monomer.
- Crosslinking is performed after polymerization or simultaneously with polymerization.
- Crosslinking carried out simultaneously with the polymerization is more preferable because the thermosetting crosslinked cyclic olefin resin film of the present invention can be obtained industrially advantageously with fewer steps.
- the term “simultaneously” as used herein means that the ring-opening metathesis polymerization reaction and the crosslinking reaction are carried out by heating in one step, and (d) the temperature at which the ring-opening metathesis polymerization catalyst is activated and (c) 1 If minute half-life temperature is 135 ⁇ 200 ° C.
- the temperature of activating i.e., (i) ring-opening metathesis polymerization reaction occurs first, and then subsequently crosslinking reaction Occurs when (ii) a crosslinking reaction occurs first, followed by a ring-opening metathesis polymerization reaction, and (iii) when the ring-opening metathesis polymerization reaction and the crosslinking reaction occur almost simultaneously, Is included in the concept.
- a cyclic olefin monomer having two or more carbon-carbon double bonds is used as a crosslinkable monomer used in the method (A).
- Specific examples of the cyclic olefin monomer are dicyclopentadiene and tricyclopentadiene.
- the crosslinking density can be controlled by the amount of the crosslinking monomer used and the heating temperature during polymerization.
- the amount of the crosslinkable monomer used is not particularly limited because appropriate crosslink density varies depending on the use of the film.
- a preferred use amount of the crosslinkable monomer is 0.1 to 100 mol% as a ratio of the crosslinkable monomer in the total amount of the cyclic olefin monomer.
- crosslinking methods include a method of irradiating a cyclic olefin polymer with light or an electron beam, and performing a crosslinking reaction after polymerization to perform crosslinking.
- the bulk polymerization and crosslinking in the present invention are preferably carried out in the absence of oxygen and water.
- Specific examples of the bulk polymerization and crosslinking methods (1) nitrogen gas, a method of performing bulk polymerization and crosslinking in the method (2) under vacuum to perform bulk polymerization and crosslinking in an inert gas atmosphere such as argon gas, (3 ) Bulk polymerization and crosslinking in a state where the composition coated on the support is covered with a resin film and sealed.
- Specific examples of the resin film are those exemplified as the support.
- the thickness of the thermosetting crosslinked cyclic olefin resin film of the present invention varies depending on the application and is not particularly limited, but is usually 0.5 to 5,000 ⁇ m, from the viewpoint of handling properties, The thickness is preferably 5 to 500 ⁇ m.
- the surface of the thermosetting crosslinked cyclic olefin resin film of the present invention may be smooth, but may have an uneven shape formed by embossing.
- the layer of a heterogeneous material such as an organic substance, an inorganic substance, or a metal is subjected to the thermosetting property of the present invention by using a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, and electroless plating. It can also form on the surface of a crosslinked cyclic olefin resin composition and a thermosetting crosslinked cyclic olefin resin film.
- a film made of a material that improves releasability such as SiO 2 , MgF 2 , or a fluororesin, may be provided on the film surface layer, or the film surface may be fluorinated by surface treatment with fluorine gas or a CF-based precursor. it can.
- the releasability is improved without performing fluorination.
- thermosetting crosslinked cyclic olefin resin composition the preferred (a) cyclic olefin monomer is a norbornene monomer.
- Preferred (b) [other than (a) and a crosslinking agent having two or more polymerizable unsaturated bonds] is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds.
- a preferable (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
- the said preferable (a) cyclic olefin monomer is a norbornene-type monomer
- preferable said (b) [other than said (a), 2 crosslinking agent having more polymerizable unsaturated bond] is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds, preferably (d) above ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
- the said preferable (a) cyclic olefin monomer is a norbornene-type monomer, preferable said (b) [other than said (a), 2 or more
- the crosslinking agent having a polymerizable unsaturated bond is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds
- the preferred (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
- thermosetting crosslinked cyclic olefin resin film The water contact angle of the resin film punched out to 50 mm x 50 mm was measured using a fully automatic contact angle meter (DM-701, Kyowa Surface Science Co., Ltd.). Then, using ion-exchanged water as a solvent, 0.6 ⁇ L (0.6 microliter) droplets were dropped and analyzed by the ⁇ / 2 method. The greater the water contact angle, the higher the water repellency.
- thermosetting crosslinked cyclic olefin resin film The tensile breaking elongation and tensile breaking strength of the thermosetting crosslinked cyclic olefin resin film were measured according to JIS K6871. The larger the tensile elongation at break of the film, the higher the sealing property of the mold, and the generation of burr of the sealing resin can be suppressed. The greater the tensile strength at break of the film, the more difficult it is to break and the leakage of the sealing resin can be suppressed.
- the sample taken out from the vacuum press was stored in an oven at 95 ° C. for 3 days, a test piece of 25 mm ⁇ 150 mm was cut out from the sample, and the 180 ° peeling force was measured according to JIS K 6854-2.
- the peeling force was defined as a prepreg peeling force after heating. The smaller the prepreg peel force is, the higher the releasability.
- Examples 1 to 13 and Comparative Examples 1 to 15 The crosslinking agent and stabilizer having two or more polymerizable unsaturated bonds in the masses shown in Tables 1 and 2 are composed of 92.6% by mass of dicyclopentadiene and 7.4% by mass of 5-ethyl-2-norbornene.
- a reaction stock solution was obtained by dissolving in a norbornene monomer mixture.
- the ruthenium catalyst having the structure of the formula (7) of the mass shown in Table 1 and Table 2 and the organic peroxide thermal polymerization initiator are added to the reaction stock solution, mixed with a line mixer, and 25 ° C.
- Examples 1 to 13 obtained from a polymerizable composition containing a crosslinking agent having two or more polymerizable unsaturated bonds and an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute
- the mold film had high initial release property, release property after heating, mechanical strength, water repellency and high-temperature discoloration resistance.
- Thermosetting property of Comparative Example 1 obtained from a polymerizable composition containing no crosslinking agent having two or more polymerizable unsaturated bonds and an organic peroxide-based thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute.
- the cross-linked cyclic olefin resin film had low water repellency, initial release property, release property after heating, and high-temperature discoloration resistance.
- thermosetting crosslinked cyclic olefin resin film of Example 2 had low water repellency, release property after heating, and mechanical strength.
- thermosetting crosslinked cyclic olefin resin film of Comparative Example 3 thus obtained had low water repellency, initial release property, release property after heating, and high-temperature discoloration resistance.
- thermosetting crosslinked cyclic olefin resin film of Comparative Example 4 was brittle, and its physical properties could not be measured.
- thermosetting crosslinked cyclic olefin resin film of Example 7 had low water repellency, initial release property, release property after heating, and high-temperature discoloration resistance.
- thermosetting crosslinked cyclic olefin resin films of Comparative Examples 8 and 9 thus obtained had low water repellency, initial release property, release property after heating, and high temperature discoloration resistance.
- thermosetting crosslinked cyclic olefin resin film of Comparative Example 10 was brittle, and its physical properties could not be measured.
- thermosetting crosslinked cyclic olefin resin films of Examples 11 to 13 were low.
- thermosetting crosslinked cyclic olefin resin composition of the present invention provides a film that is suitably used for a semiconductor sealing step in the manufacture of a semiconductor device.
- the method for carrying out semiconductor encapsulation using the thermosetting crosslinked cyclic olefin resin film of the present invention is not particularly limited.
- Specific examples of the semiconductor sealing method include: (I) Resin sealing with a release film interposed between a lead frame on which a semiconductor chip is mounted and a mold inner surface on one side so as to contact the lead frame substrate. Method (II) The lead frame substrate on which the semiconductor chip is mounted is separated so that the sealing material is filled between the semiconductor chip surface and at least one mold inner surface between the chip and the mold at the time of sealing.
- a mold film is interposed for resin sealing, that is, a release film is interposed on at least one side of the upper mold and the lower mold inner surface.
- thermosetting cross-linked cyclic olefin resin composition of the present invention utilizes the property of having excellent water repellency even if it does not contain a fluorine component and a silicone component containing fluorine in the molecule. It is formed into various molded bodies other than the process film.
- the thermosetting crosslinked cyclic olefin resin film of the present invention is suitably used as a release film at the time of manufacturing a printed circuit board and at the time of a cover-laying step for a flexible printed circuit board.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-エチルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-シクロヘキシルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-シクロペンチルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-メチレンテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-エチリデンテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-ビニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-プロペニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-シクロヘキセニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-シクロペンテニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン、9-フェニルテトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エンなどの非極性のテトラシクロドデセン類;
2-ノルボルネン、5-メチル-2-ノルボルネン、5-エチル-2-ノルボルネン、5-ブチル-2-ノルボルネン、5-ヘキシル-2-ノルボルネン、5-デシル-2-ノルボルネン、5-シクロヘキシル-2-ノルボルネン、5-シクロペンチル-2-ノルボルネン、5-エチリデン-2-ノルボルネン、5-ビニル-2-ノルボルネン、5-プロペニル-2-ノルボルネン、5-シクロヘキセニル-2-ノルボルネン、5-シクロペンテニル-2-ノルボルネン、5-フェニル-2-ノルボルネン、テトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(1,4-メタノ-1,4,4a,9a-テトラヒドロ-9H-フルオレンとも言う。)、テトラシクロ[10.2.1.02,11.04,9]ペンタデカ-4,6,8,13-テトラエン(1,4-メタノ-1,4,4a,9,9a,10-ヘキサヒドロアントラセンとも言う。)などの非極性のノルボルネン類;
ペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカ-4,10-ジエン、ペンタシクロ[9.2.1.14,7.02,10.03,8]ペンタデカ-5,12-ジエン、ヘキサシクロ[6.6.1.13,6.110,13.02,7.09,14]ヘプタデカ-4-エンなどの五環体以上の非極性の環状オレフィン類;などである。 Specific examples of the nonpolar norbornene-based monomer include nonpolar such as dicyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.02,6] dec-8-ene). Of dicyclopentadiene;
Tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-methyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9- Ethyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-methylenetetracyclo [6.2.13,6.02,7] dodec-4- Ene, 9-ethylidenetetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-vinyltetracyclo [6.2.13,6.02,7] dodeca 4-ene, 9-propenyltetracyclo [6.2.13, 6.02,7] dodec-4-e 9-cyclohexenyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-cyclopentenyltetracyclo [6.2.1.13,6.02,7] dodeca Nonpolar tetracyclododecenes such as -4-ene, 9-phenyltetracyclo [6.2.1.13, 6.02,7] dodec-4-ene;
2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2- Norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2- Norbornene, 5-phenyl-2-norbornene, tetracyclo [9.2.1.02,10.03,8] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene)), tetracyclo [10.2.1.02, 11. 4,9] pentadeca -4,6,8,13- tetraene (. 1,4-methano -1,4,4a, 9, 9a, also referred to as 10-hexa hydro anthracene) nonpolar norbornene, such as;
Pentacyclo [6.5.1.13, 6.02, 7.09, 13] pentadeca-4,10-diene, pentacyclo [9.2.14, 7.02, 10.03,8] pentadeca Non-polar cyclic olefins having five or more rings such as 5,12-diene, hexacyclo [6.6.1.13, 6.110, 13.02, 7.09,14] heptade-4-ene; It is.
ベンジリデンビス(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(3-メチル-2-ブテン-1-イリデン)ビス(トリシクロペンチルホスフィン)ルテニウムジクロリドなどの、2つの中性電子供与性化合物が結合したルテニウム錯体化合物;
ベンジリデンビス(1,3-ジシクロヘキシル-4-イミダゾリジン-2-イリデン)ルテニウムジクロリド、ベンジリデンビス(1,3-ジイソプロピル-4-イミダゾリン-2-イリデン)ルテニウムジクロリドなどの、2つのヘテロ原子含有カルベン化合物が結合したルテニウム錯体化合物;
式(6)で表される、X2とL2が互いに結合して多座キレート化配位子を形成しているルテニウムカルベン錯体;などである。 Specific examples of the complex compound represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4). , 5-Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-octahydrobenzimida 2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3 -Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H -1,2,4-triazol-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene 1,3-dimesityl-4-imidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride Lori A ruthenium complex compound in which one hetero atom-containing carbene compound and one neutral electron donating compound are bonded, such as
A ruthenium complex compound in which two neutral electron-donating compounds are bonded, such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride;
Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexyl-4-imidazolidin-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium complex compound in which is bonded;
A ruthenium carbene complex represented by formula (6) in which X 2 and L 2 are bonded to each other to form a multidentate chelating ligand;
50mm×50mmに打ち抜かれた樹脂フィルムの水接触角を、全自動接触角計(協和表面科学(株)製DM-701)を使用し、溶媒としてイオン交換水を使用し、0.6μL(0.6マイクロリットル)の液滴を滴下して、θ/2法で解析した。水接触角が大きいほど、撥水性が高い。 (1) Water contact angle of thermosetting crosslinked cyclic olefin resin film The water contact angle of the resin film punched out to 50 mm x 50 mm was measured using a fully automatic contact angle meter (DM-701, Kyowa Surface Science Co., Ltd.). Then, using ion-exchanged water as a solvent, 0.6 μL (0.6 microliter) droplets were dropped and analyzed by the θ / 2 method. The greater the water contact angle, the higher the water repellency.
熱硬化性架橋環状オレフィン樹脂フィルムの引張破断伸び及び引張破断強度をJIS K6871に準拠して測定した。フィルムの引張破断伸びが大きいほど、金型の密閉性が高くなり、封止樹脂のバリの生成を抑制できる。フィルムの引張破断強度が大きいほど、フィルムは破れ難く、封止樹脂の漏れを抑制できる。 (2) Tensile properties of thermosetting crosslinked cyclic olefin resin film The tensile breaking elongation and tensile breaking strength of the thermosetting crosslinked cyclic olefin resin film were measured according to JIS K6871. The larger the tensile elongation at break of the film, the higher the sealing property of the mold, and the generation of burr of the sealing resin can be suppressed. The greater the tensile strength at break of the film, the more difficult it is to break and the leakage of the sealing resin can be suppressed.
300mm×300mmに打ち抜かれたプリント基板積層用プリプレグ(パナソニック電工(株)製FR-4 R-1661(G)GBタイプ)の両面を、各実施例又は比較例の離型フィルムではさんで真空プレス中に挿入し、1.0MPa、180℃で70分間加熱硬化した後、40℃まで冷却して、得られた試料を真空プレスから取り出した。25mm×150mmの試験片を当該試料から切り出し、180度剥離力をJIS K 6854-2に従って測定した。当該剥離力を初期対プリプレグ剥離力とした。 (3) Peeling force against prepreg of thermosetting crosslinked cyclic olefin resin film Both sides of prepreg for printed circuit board lamination (FR-4 R-1661 (G) GB type manufactured by Panasonic Electric Works Co., Ltd.) punched out to 300 mm x 300 mm The sample was inserted into a vacuum press sandwiched between the release films of each Example or Comparative Example, heated and cured at 1.0 MPa and 180 ° C. for 70 minutes, cooled to 40 ° C., and the obtained sample was removed from the vacuum press. I took it out. A test piece of 25 mm × 150 mm was cut out from the sample, and the 180 ° peel force was measured according to JIS K 6854-2. The peel force was defined as initial prepreg peel force.
50mm×150mmに打ち抜かれた樹脂フィルムを95℃のオーブンに3日間保存して取り出し、取り出したフィルムの色差をコニカミノルタセンシング(株)製色彩色差計CR-400を使用して測定した。値が小さいほど、高温耐変色性が高い。 (4) Discoloration after heating of thermosetting crosslinked cyclic olefin resin film The resin film punched out to 50 mm x 150 mm was stored in an oven at 95 ° C for 3 days and taken out, and the color difference of the taken out film was manufactured by Konica Minolta Sensing Co., Ltd. Measurement was performed using a color difference meter CR-400. The smaller the value, the higher the high temperature discoloration resistance.
表1及び表2に示される質量の2以上の重合性不飽和結合を有する架橋剤、安定剤を、ジシクロペンタジエン92.6質量%及び5-エチル-2-ノルボルネン7.4質量%からなるノルボルネン系モノマー混合液に溶解して反応原液を得た。次に、表1及び表2に示される質量の式(7)の構造を有するルテニウム触媒、有機過酸化物系熱重合開始剤を上記反応原液に添加し、ラインミキサーで混合し、25℃で、厚さ0.075mmのポリエチレンテレフタレート製キャリアフィルム上に塗工しキャスト製膜を行い、次いで直ぐに、塗布層の上から別に用意した上記同様のキャリアフィルムをラミネートした。その後、200℃で3分間加熱を行い、開環メタセシス重合及び架橋を行わせ、樹脂フィルムを得た。 Examples 1 to 13 and Comparative Examples 1 to 15
The crosslinking agent and stabilizer having two or more polymerizable unsaturated bonds in the masses shown in Tables 1 and 2 are composed of 92.6% by mass of dicyclopentadiene and 7.4% by mass of 5-ethyl-2-norbornene. A reaction stock solution was obtained by dissolving in a norbornene monomer mixture. Next, the ruthenium catalyst having the structure of the formula (7) of the mass shown in Table 1 and Table 2 and the organic peroxide thermal polymerization initiator are added to the reaction stock solution, mixed with a line mixer, and 25 ° C. Then, coating was performed on a carrier film made of polyethylene terephthalate having a thickness of 0.075 mm to form a cast film, and immediately thereafter, a carrier film similar to the above prepared separately from above the coating layer was laminated. Then, it heated at 200 degreeC for 3 minute (s), ring-opening metathesis polymerization and bridge | crosslinking were performed, and the resin film was obtained.
2)BASFジャパン(株)製IRGANOX1010
3)(株)ADEKA製アデカスタブHP-10
4)BASFジャパン(株)製TINUVIN770
5)化薬アクゾ(株)製カヤレン6-70 1分間半減温度150℃
6)日油(株)製パーロイルTCP 1分間半減温度92.1℃
7)日油(株)製ナイパーE 1分間半減温度130℃
8)化薬アクゾ(株)製パーカドックス14R-G 1分間半減温度185℃
9)共栄社化学(株)製ライトエステルTMP
10)共栄社化学(株)製ライトアクリレートPE-3A
11)共栄社化学(株)製ライトアクリレートDPE-6A
12)新中村化学工業(株)製NKエステルA-DCP
13)新中村化学工業(株)製NKエステルA-200
14)新中村化学工業(株)製NKエステルA-400
15)RIMTEC(株)製VC843
2以上の重合性不飽和結合を有する架橋剤及び1分間半減温度が135~200℃の有機過酸化物系熱重合開始剤を含有した重合性組成物から得られた実施例1~13の離型フィルムの初期離型性、加熱後離型性、機械的強度、撥水性及び高温耐変色性は高かった。 1) IRGANOX565 manufactured by BASF Japan
2) IRGANOX1010 manufactured by BASF Japan
3) ADEKA Corporation ADK STAB HP-10
4) TINUVIN770 manufactured by BASF Japan
5) Kayalen 6-70 manufactured by Kayaku Akzo Co., Ltd. 1 minute half temperature 150 ° C
6) NOF Corporation Parroyl TCP 1 minute half temperature 92.1 ° C
7) Nipa Nipper E 1 minute half-temperature 130 ° C
8) Perkadox 14R-G manufactured by Kayaku Akzo Co., Ltd. 1 minute half-temperature 185 ° C
9) Kyoeisha Chemical Co., Ltd. light ester TMP
10) Light acrylate PE-3A manufactured by Kyoeisha Chemical Co., Ltd.
11) Kyoeisha Chemical Co., Ltd. light acrylate DPE-6A
12) NK Ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.
13) NK Ester A-200 manufactured by Shin-Nakamura Chemical Co., Ltd.
14) NK Ester A-400 manufactured by Shin-Nakamura Chemical Co., Ltd.
15) VC843 manufactured by RIMTEC Corporation
Separation of Examples 1 to 13 obtained from a polymerizable composition containing a crosslinking agent having two or more polymerizable unsaturated bonds and an organic peroxide thermal polymerization initiator having a half-temperature of 135 to 200 ° C. for 1 minute The mold film had high initial release property, release property after heating, mechanical strength, water repellency and high-temperature discoloration resistance.
本発明の熱硬化性架橋環状オレフィン樹脂フィルムは、プリント基板製造時及びフレキシブルプリント基板のカバーレイ貼付工程時の離型フィルムとして好適に使用される。 Furthermore, the thermosetting cross-linked cyclic olefin resin composition of the present invention utilizes the property of having excellent water repellency even if it does not contain a fluorine component and a silicone component containing fluorine in the molecule. It is formed into various molded bodies other than the process film.
The thermosetting crosslinked cyclic olefin resin film of the present invention is suitably used as a release film at the time of manufacturing a printed circuit board and at the time of a cover-laying step for a flexible printed circuit board.
Claims (15)
- (a)環状オレフィンモノマー100質量部、(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]0.7~40質量部、(c)1分間半減温度が135~200℃の有機過酸化物系熱重合開始剤1.15~15質量部及び(d)開環メタセシス重合触媒を含有する重合性組成物を加熱して開環メタセシス重合及び架橋して得られる熱硬化性架橋環状オレフィン樹脂組成物。 (A) 100 parts by mass of a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds], 0.7 to 40 parts by mass, (c) half-temperature for 1 minute A polymerizable composition containing 1.15 to 15 parts by mass of an organic peroxide thermal polymerization initiator at 135 to 200 ° C. and (d) a ring-opening metathesis polymerization catalyst is heated to perform ring-opening metathesis polymerization and crosslinking. The thermosetting crosslinked cyclic olefin resin composition obtained.
- 上記(a)環状オレフィンモノマーがノルボルネン系モノマーである、請求項1に記載されている熱硬化性架橋環状オレフィン樹脂組成物。 The thermosetting crosslinked cyclic olefin resin composition according to claim 1, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.
- 上記(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]が、2以上の重合性不飽和結合を有する(メタ)アクリル酸エステルである、請求項1又は2に記載されている熱硬化性架橋環状オレフィン樹脂組成物。 The (b) [other than (a) and a crosslinking agent having two or more polymerizable unsaturated bonds] is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds. Or the thermosetting crosslinked cyclic olefin resin composition described in 2.
- 上記(d)開環メタセシス重合触媒がルテニウムカルベン錯体である、請求項1~3のいずれか1項に記載されている熱硬化性架橋環状オレフィン樹脂組成物。 The thermosetting crosslinked cyclic olefin resin composition according to any one of claims 1 to 3, wherein the (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
- 請求項1~4のいずれか1項に記載されている熱硬化性架橋環状オレフィン樹脂組成物からなる熱硬化性架橋環状オレフィン樹脂フィルム。 A thermosetting crosslinked cyclic olefin resin film comprising the thermosetting crosslinked cyclic olefin resin composition according to any one of claims 1 to 4.
- 半導体封止工程に用いられる離型フィルムである、請求項5に記載されている熱硬化性架橋環状オレフィン樹脂フィルム。 The thermosetting crosslinked cyclic olefin resin film according to claim 5, which is a release film used in a semiconductor sealing process.
- プリント基板製造用の離型フィルムである、請求項5に記載されている熱硬化性架橋環状オレフィン樹脂フィルム。 The thermosetting crosslinked cyclic olefin resin film according to claim 5, which is a release film for producing a printed circuit board.
- (a)環状オレフィンモノマー100質量部、(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]0.7~40質量部、(c)1分間半減温度が135~200℃の有機過酸化物系熱重合開始剤1.15~15質量部及び(d)開環メタセシス重合触媒を含有する重合性組成物を加熱して開環メタセシス重合及び架橋する工程を含む、請求項1に記載されている熱硬化性架橋環状オレフィン樹脂組成物の製造方法。 (A) 100 parts by mass of a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds], 0.7 to 40 parts by mass, (c) half-temperature for 1 minute A step of heating a polymerizable composition containing 1.15 to 15 parts by mass of an organic peroxide thermal polymerization initiator having a temperature of 135 to 200 ° C. and (d) a ring-opening metathesis polymerization catalyst and crosslinking The manufacturing method of the thermosetting crosslinked cyclic olefin resin composition described in Claim 1 containing this.
- 上記(a)環状オレフィンモノマーがノルボルネン系モノマーである、請求項8に記載されている熱硬化性架橋環状オレフィン樹脂組成物の製造方法。 The method for producing a thermosetting crosslinked cyclic olefin resin composition according to claim 8, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.
- 上記(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]が、2以上の重合性不飽和結合を有する(メタ)アクリル酸エステルである、請求項8又は9に記載されている熱硬化性架橋環状オレフィン樹脂組成物の製造方法。 9. The (b) [other than (a) and a cross-linking agent having two or more polymerizable unsaturated bonds] is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds. Or 9. A method for producing a thermosetting crosslinked cyclic olefin resin composition described in 9.
- 上記(d)開環メタセシス重合触媒がルテニウムカルベン錯体である、請求項8~10のいずれか1項に記載されている熱硬化性架橋環状オレフィン樹脂組成物の製造方法。 The method for producing a thermosetting crosslinked cyclic olefin resin composition according to any one of claims 8 to 10, wherein the (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
- (a)環状オレフィンモノマー100質量部、(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]0.7~40質量部、(c)1分間半減温度が135~200℃の有機過酸化物系熱重合開始剤1.15~15質量部及び(d)開環メタセシス重合触媒を含有する重合性組成物を支持体上に塗布し、加熱して開環メタセシス重合及び架橋を上記支持体上で行う工程を含む、請求項5に記載されている熱硬化性架橋環状オレフィン樹脂フィルムの製造方法。 (A) 100 parts by mass of a cyclic olefin monomer, (b) [a crosslinking agent other than the above (a) and having two or more polymerizable unsaturated bonds], 0.7 to 40 parts by mass, (c) half-temperature for 1 minute A polymerizable composition containing 1.15 to 15 parts by mass of an organic peroxide thermal polymerization initiator having a temperature of 135 to 200 ° C. and (d) a ring-opening metathesis polymerization catalyst is applied onto a support and heated to open. The method for producing a thermosetting crosslinked cyclic olefin resin film according to claim 5, comprising a step of performing ring metathesis polymerization and crosslinking on the support.
- 上記(a)環状オレフィンモノマーがノルボルネン系モノマーである、請求項12に記載されている熱硬化性架橋環状オレフィン樹脂フィルムの製造方法。 The method for producing a thermosetting crosslinked cyclic olefin resin film according to claim 12, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.
- 上記(b)[前記(a)以外であり、2以上の重合性不飽和結合を有する架橋剤]が、2以上の重合性不飽和結合を有する(メタ)アクリル酸エステルである、請求項12又は13に記載されている熱硬化性架橋環状オレフィン樹脂フィルムの製造方法。 The (b) [other than (a) and a crosslinking agent having two or more polymerizable unsaturated bonds] is a (meth) acrylic acid ester having two or more polymerizable unsaturated bonds. Alternatively, a method for producing a thermosetting crosslinked cyclic olefin resin film described in Item 13.
- 上記(d)開環メタセシス重合触媒がルテニウムカルベン錯体である、請求項12~14のいずれか1項に記載されている熱硬化性架橋環状オレフィン樹脂フィルムの製造方法。 The method for producing a thermosetting crosslinked cyclic olefin resin film according to any one of claims 12 to 14, wherein the (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013507074A JPWO2012132150A1 (en) | 2011-03-28 | 2011-12-23 | Thermosetting crosslinked cyclic olefin resin composition, thermosetting crosslinked cyclic olefin resin film, method for producing thermosetting crosslinked cyclic olefin resin composition, and method for producing thermosetting crosslinked cyclic olefin resin film |
CN2011800580389A CN103221453A (en) | 2011-03-28 | 2011-12-23 | Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin |
KR1020137013620A KR20130118332A (en) | 2011-03-28 | 2011-12-23 | Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin resin film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011069347 | 2011-03-28 | ||
JP2011-069347 | 2011-03-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012132150A1 true WO2012132150A1 (en) | 2012-10-04 |
Family
ID=46929947
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/079945 WO2012132150A1 (en) | 2011-03-28 | 2011-12-23 | Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin resin film |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPWO2012132150A1 (en) |
KR (1) | KR20130118332A (en) |
CN (1) | CN103221453A (en) |
TW (1) | TW201238992A (en) |
WO (1) | WO2012132150A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014045712A1 (en) * | 2012-09-21 | 2014-03-27 | 日本ゼオン株式会社 | Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film and method for producing same |
WO2014087772A1 (en) * | 2012-12-07 | 2014-06-12 | 太陽ホールディングス株式会社 | Crosslinkable resin composition, cured product and method for producing same |
JP2014151483A (en) * | 2013-02-06 | 2014-08-25 | Daicel Corp | Release film, method for producing the same and application therefor |
JP2016089023A (en) * | 2014-11-04 | 2016-05-23 | 日本ゼオン株式会社 | Method for producing water-repellent film |
EP3070770A4 (en) * | 2013-11-14 | 2017-05-24 | Daicel Corporation | Release film, laminate and method for manufacturing same, and method for manufacturing fuel cell |
WO2022070871A1 (en) * | 2020-09-29 | 2022-04-07 | 日本ゼオン株式会社 | Negative photosensitive resin composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5922292B1 (en) * | 2015-02-16 | 2016-05-24 | 住友化学株式会社 | Curable adhesive composition and polarizing plate using the same |
WO2022030310A1 (en) * | 2020-08-03 | 2022-02-10 | Rimtec株式会社 | Cycloolefin resin cured product |
CN112876688B (en) * | 2021-01-20 | 2022-10-28 | 浙江理工大学 | Preparation method of nano micelle suitable for tandem catalysis |
CN113583264A (en) * | 2021-07-09 | 2021-11-02 | 镇江高美新材料有限公司 | Cross-linking vulcanization method of silicone rubber |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000051178A1 (en) * | 1999-02-26 | 2000-08-31 | Hitachi Chemical Company, Ltd. | Electronic device |
WO2005017033A1 (en) * | 2003-08-13 | 2005-02-24 | Zeon Corporation | Crosslinkable resin composition and resin formed body produced therefrom |
JP2006257399A (en) * | 2005-02-21 | 2006-09-28 | Kureha Corp | Mold release film, laminated mold release film and methods for producing them |
JP2008143956A (en) * | 2006-12-06 | 2008-06-26 | Nippon Zeon Co Ltd | Polymerizable composition, crosslinkable resin and method for producing the same |
JP2008150569A (en) * | 2006-11-22 | 2008-07-03 | Nippon Zeon Co Ltd | Polymerizable composition and crosslinkable resin and method for producing the same |
JP2009242720A (en) * | 2008-03-31 | 2009-10-22 | Nippon Zeon Co Ltd | Polymerizable composition containing cycloolefin monomer having two or more unsaturated bonds in molecule and at least one of bonds thereof being metathesis-reactive, prepreg, and laminate product using it |
WO2010147116A1 (en) * | 2009-06-15 | 2010-12-23 | 日本ゼオン株式会社 | Polymerizable composition, resin molded body, and laminate |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007137981A (en) * | 2005-11-17 | 2007-06-07 | Nippon Zeon Co Ltd | Mold release film and method for producing the same |
JP5180826B2 (en) * | 2006-06-27 | 2013-04-10 | 三井化学株式会社 | Film and release film |
-
2011
- 2011-12-23 KR KR1020137013620A patent/KR20130118332A/en not_active Application Discontinuation
- 2011-12-23 JP JP2013507074A patent/JPWO2012132150A1/en active Pending
- 2011-12-23 WO PCT/JP2011/079945 patent/WO2012132150A1/en active Application Filing
- 2011-12-23 CN CN2011800580389A patent/CN103221453A/en active Pending
-
2012
- 2012-01-16 TW TW101101527A patent/TW201238992A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000051178A1 (en) * | 1999-02-26 | 2000-08-31 | Hitachi Chemical Company, Ltd. | Electronic device |
WO2005017033A1 (en) * | 2003-08-13 | 2005-02-24 | Zeon Corporation | Crosslinkable resin composition and resin formed body produced therefrom |
JP2006257399A (en) * | 2005-02-21 | 2006-09-28 | Kureha Corp | Mold release film, laminated mold release film and methods for producing them |
JP2008150569A (en) * | 2006-11-22 | 2008-07-03 | Nippon Zeon Co Ltd | Polymerizable composition and crosslinkable resin and method for producing the same |
JP2008143956A (en) * | 2006-12-06 | 2008-06-26 | Nippon Zeon Co Ltd | Polymerizable composition, crosslinkable resin and method for producing the same |
JP2009242720A (en) * | 2008-03-31 | 2009-10-22 | Nippon Zeon Co Ltd | Polymerizable composition containing cycloolefin monomer having two or more unsaturated bonds in molecule and at least one of bonds thereof being metathesis-reactive, prepreg, and laminate product using it |
WO2010147116A1 (en) * | 2009-06-15 | 2010-12-23 | 日本ゼオン株式会社 | Polymerizable composition, resin molded body, and laminate |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014045712A1 (en) * | 2012-09-21 | 2014-03-27 | 日本ゼオン株式会社 | Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film and method for producing same |
WO2014087772A1 (en) * | 2012-12-07 | 2014-06-12 | 太陽ホールディングス株式会社 | Crosslinkable resin composition, cured product and method for producing same |
JPWO2014087772A1 (en) * | 2012-12-07 | 2017-01-05 | 太陽ホールディングス株式会社 | Cross-linked resin composition, cured product and method for producing the same |
JP2014151483A (en) * | 2013-02-06 | 2014-08-25 | Daicel Corp | Release film, method for producing the same and application therefor |
EP3070770A4 (en) * | 2013-11-14 | 2017-05-24 | Daicel Corporation | Release film, laminate and method for manufacturing same, and method for manufacturing fuel cell |
US10622658B2 (en) | 2013-11-14 | 2020-04-14 | Daicel Corporation | Release film, laminate and method for manufacturing same, and method for manufacturing fuel cell |
JP2016089023A (en) * | 2014-11-04 | 2016-05-23 | 日本ゼオン株式会社 | Method for producing water-repellent film |
WO2022070871A1 (en) * | 2020-09-29 | 2022-04-07 | 日本ゼオン株式会社 | Negative photosensitive resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPWO2012132150A1 (en) | 2014-07-24 |
TW201238992A (en) | 2012-10-01 |
KR20130118332A (en) | 2013-10-29 |
CN103221453A (en) | 2013-07-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012132150A1 (en) | Thermosetting crosslinked cycloolefin resin composition, thermosetting crosslinked cycloolefin resin film, process for producing thermosetting crosslinked cycloolefin resin composition, and process for producing thermosetting crosslinked cycloolefin resin film | |
JP2013185141A (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP2012007117A (en) | Thermosetting crosslinked cyclic olefin resin film and its manufacturing method | |
JPWO2013035499A1 (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
WO2012063579A1 (en) | Thermosetting crosslinked cycloolefin resin film and manufacturing process therefor | |
JP2014136350A (en) | Laminate and method for manufacturing the same | |
JP2014136728A (en) | Crosslinked cycloolefin resin film, laminate, and method for manufacturing the same | |
JPWO2013175894A1 (en) | Cross-linked cyclic olefin resin film, laminate and production method thereof | |
JPWO2014045712A1 (en) | Cross-linked cyclic olefin resin composition, cross-linked cyclic olefin resin film, and production method thereof | |
JP2014136727A (en) | Crosslinked cycloolefin resin composition, crosslinked cycloolefin resin film, and methods for manufacturing both | |
JP2012188562A (en) | Thermoset crosslinked cyclic olefin resin film, and method for manufacturing the same | |
JP5605276B2 (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP5382363B2 (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP2012102274A (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JPWO2013175893A1 (en) | Cross-linked cyclic olefin resin film, laminate and production method thereof | |
JP2014205792A (en) | Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film and method of producing the same | |
JP2013100416A (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP2013185067A (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP2013151596A (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same | |
JP2014221876A (en) | Crosslinked cycloolefin resin composition, crosslinked cycloolefin resin film and method of producing the same | |
JP2015003962A (en) | Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film, and production method of the same | |
JP2014024963A (en) | Cross-linked cycloolefin resin film, laminate, and method for manufacturing laminate | |
JP2013151597A (en) | Heat-curable crosslinked cyclic olefin resin film and method for producing the same | |
JP2014162840A (en) | Crosslinked cycloolefin resin composition, crosslinked cycloolefin resin film, and methods for producing the same | |
JPWO2013136963A1 (en) | Thermosetting crosslinked cyclic olefin resin film and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11862417 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013507074 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20137013620 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11862417 Country of ref document: EP Kind code of ref document: A1 |