WO2017187783A1 - Composition de résine thermodurcissable, objet durci, matériau de moulage et objet moulé - Google Patents

Composition de résine thermodurcissable, objet durci, matériau de moulage et objet moulé Download PDF

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WO2017187783A1
WO2017187783A1 PCT/JP2017/008472 JP2017008472W WO2017187783A1 WO 2017187783 A1 WO2017187783 A1 WO 2017187783A1 JP 2017008472 W JP2017008472 W JP 2017008472W WO 2017187783 A1 WO2017187783 A1 WO 2017187783A1
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group
resin composition
molecule
thermosetting resin
bis
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PCT/JP2017/008472
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Japanese (ja)
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聖司 西岡
悠策 増原
長明 趙
大塚　恵子
木村　肇
松本　明博
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住友精化株式会社
アドバンスト・ソフトマテリアルズ株式会社
地方独立行政法人 大阪市立工業研究所
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Priority to JP2018514166A priority Critical patent/JP6987745B2/ja
Publication of WO2017187783A1 publication Critical patent/WO2017187783A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/10—Polymers provided for in subclass C08B
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

Definitions

  • the present invention relates to a thermosetting resin composition. Moreover, this invention relates to the hardened
  • epoxy resins have been widely used as sealing materials for electronic devices because of their advantages such as low warpage, low stress, high thermal conductivity, and high insulation.
  • it has become difficult for conventional epoxy resins to satisfy requirements regarding heat resistance and the like.
  • silicon carbide elements and gallium nitride elements has been promoted, and operation of these elements at a temperature of 200 ° C. or higher is required. Yes. Therefore, a new sealing material that can cope with the operation guarantee at a temperature of 200 ° C. or higher has been demanded, and maleimide resin has attracted attention as a sealing material that replaces the epoxy resin.
  • the maleimide resin has high heat resistance and excellent dimensional stability, but generally has a drawback that the obtained cured product is brittle.
  • a method for improving this defect a method of improving the molecular structure of maleimide resin (Patent Document 1) and a method of adding rubber or thermoplastic resin (Patent Documents 2 and 3) are disclosed.
  • An object of this invention is to provide the thermosetting resin composition which can obtain the hardened
  • the present invention relates to a polyrotaxane comprising a compound having a maleimide group, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule.
  • a thermosetting resin composition Is a thermosetting resin composition.
  • the present inventors have found that a cured product having excellent mechanical strength, heat resistance, and toughness can be obtained by using a compound having a maleimide group and a polyrotaxane in combination, and the present invention has been completed. It was.
  • the thermosetting resin composition of the present invention contains a compound having a maleimide group (hereinafter also referred to as “maleimide compound”).
  • maleimide compound a compound having a maleimide group
  • a polyimide compound obtained by condensing tetracarboxylic dianhydride and diamine molecules grow linearly.
  • This polyimide compound has high strength and is mainly excellent in adhesion to metals.
  • it is used for flexible copper-clad laminates, but voids (bubbles) are easily generated due to by-product of water and alcohol during curing. There is a problem that.
  • the maleimide compound used in the thermosetting resin composition of the present invention has the advantage that there is no by-product and no voids are generated because curing proceeds by an addition reaction.
  • the maleimide compound is excellent in strength, and in the curing reaction, the molecule grows in a three-dimensional network structure. Therefore, in addition to the metal, the maleimide compound has excellent adhesion to a wide range of materials such as glass and organic materials. It is used in glass-based copper-clad laminates and organic-based copper-clad laminates.
  • the thermosetting resin composition of the present invention can impart high toughness to a cured product while maintaining the excellent characteristics of the maleimide compound described above by using such a maleimide compound and a polyrotaxane in combination. Further expansion of applications can be expected.
  • the maleimide compound preferably has two or more maleimide groups in one molecule. By having two or more maleimide groups in one molecule, a three-dimensional network structure can be easily formed, and a cured product having higher heat resistance can be obtained.
  • the maleimide compound is preferably a maleimide compound having an aromatic ring.
  • Examples of the compound having two or more maleimide groups in one molecule include compounds represented by the following formula (1).
  • Z is a divalent or higher residue, and n is an integer of 2 or higher.
  • examples of the divalent or higher-valent residue represented by Z include, for example, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 9 carbon atoms, a phenylene group, a naphthalene group, and benzenetriyl.
  • a compound represented by the following formula (2) and a compound represented by the following formula (3) are preferable from the viewpoint of heat resistance of the cured product.
  • cured material other than the compound represented by said Formula (1) is preferable.
  • Y represents a bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N ⁇ N—, —N ⁇ C ⁇ N—, —C ( ⁇ O) —, —SO 2 —, —S ( ⁇ O) —, —O—, —S—, a divalent substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a divalent substituted or unsubstituted aromatic hydrocarbon group
  • R 1 and R 2 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group
  • o and p are each independently an integer of 0 to 4. When o is 2 or more, the plurality of R 1 may be the same or different, and when p is 2 or more, the plurality of R 2 may be the same. And may be different.
  • R 3 is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group, and q is 0 to It is an integer of 4. When q is 2 or more, the plurality of R 3 may be the same or different.
  • R 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group
  • r is 0 ⁇ It is an integer of 3, and m is 2 or more. When r is 2 or more, the plurality of R 4 may be the same or different.
  • substituents include a halogen group, a hydroxy group, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, an acyloxy group, an acyl group, and a heterocyclic group.
  • maleimide compound examples include 4,4′-bismaleimide biphenyl, bis (4-maleimidophenyl) methane, bis (3-maleimidophenyl) methane, bis (4-maleimidocyclohexyl) methane, and bis ( 3-maleimidocyclohexyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis ( 3,5-diethyl-4-maleimidophenyl) methane, bis (3-propyl-4-maleimidophenyl) methane, bis (3,5-dipropyl-4-maleimidophenyl) methane, bis (3-butyl-4-maleimide) Phenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl)
  • maleimide compounds may be used alone or in combination of two or more.
  • the maleimide group of the compound having two or more maleimide groups in one molecule is preferably present at a position where the molecule has line symmetry from the viewpoint of heat resistance of the cured product.
  • the maleimide compound may have an alkenyl group and / or an amino group in addition to the maleimide group.
  • the maleimide compound having an alkenyl group include N-allylmaleimide, N-methacrylmaleimide, N-ethylmalemidyl methacrylate, N-ethylmalemidyl acrylate, and the like.
  • maleimide compounds having an amino group include N-aminomethylmaleimide, N- (2-aminoethyl) maleimide, N- (4-aminophenyl) maleimide and the like.
  • the minimum with preferable content of the said maleimide compound in the whole thermosetting resin composition of this invention is 30 mass%, a preferable upper limit is 95 mass%, a more preferable minimum is 50 mass%, and a more preferable upper limit is 85 mass%. It is.
  • thermosetting resin composition of the present invention comprises a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. contains.
  • the cyclic molecule is a compound that can be included so that a linear molecule penetrates like a skewer in an opening and can move on the linear molecule.
  • a conventionally known method for example, a method described in JP-A No. 2005-154675
  • cyclic of the cyclic molecule means substantially cyclic, and may be a complete ring-closed structure as long as it can move on the linear molecule. For example, a spiral structure may be used.
  • cyclic molecule examples include cyclic polymers such as cyclic polyether, cyclic polyester, and cyclic polyetheramine, pillar arenes, cyclophanes, ring-expanded porphyrins, and cyclodextrins.
  • cyclic polymer examples include crown ether and derivatives thereof, calixarene and derivatives thereof, cyclophane and derivatives thereof, cryptand and derivatives thereof, and the like.
  • the cyclic molecule is appropriately selected depending on the type of linear molecule to be used, but since it is easily available and many types of blocking groups can be selected, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclo Cyclodextrins such as dextrin are preferred. For example, as will be described later, when polyethylene glycol is selected as the linear molecule, ⁇ -cyclodextrin is preferred from the viewpoint of the stability of the resulting clathrate.
  • a part of the hydroxyl group of the cyclodextrin is modified with a modifying group that improves compatibility with the maleimide compound (hereinafter also referred to as “solubility imparting group”). It is preferable.
  • solubility-imparting group examples include an acetyl group, an alkyl group having 1 to 18 carbon atoms, a trityl group, a trimethylsilyl group, a phenyl group, a polyester chain, an oxyethylene chain, and a polyacrylate chain.
  • These modifying groups may be introduced alone or two or more of them may be introduced.
  • the hydroxyl group of the cyclodextrins is first modified with an oxyethylene chain, and the introduced hydroxyl group at the end of the oxyethylene chain is changed.
  • a method of introducing a polyester chain or the like can be used. Specifically, after adding a hydroxypropyl group to the hydroxyl group present in the cyclodextrin itself, ring-opening polymerization of ⁇ -caprolactone through the hydroxyl group of the hydroxypropyl group to introduce a polycaprolactone (polyester) chain. Can do.
  • the introduction rate of the solubility-imparting group is preferably 10 mol%, preferably the upper limit with respect to the total hydroxyl groups of the cyclodextrins when cyclodextrins are used as the cyclic molecules. Is 90 mol%, a more preferred lower limit is 30 mol%, and a more preferred upper limit is 70 mol%.
  • the polyrotaxane contained in the thermosetting resin composition of the present invention may have a substituent that can directly participate in the thermosetting reaction (hereinafter also referred to as “curing reactive substituent”).
  • the curing reactive substituent may be directly introduced into a cyclic molecule, for example, a hydroxyl group of cyclodextrins, or the terminal reactive site of the solubility-imparting group, For example, after a hydroxypropyl group is added to the hydroxyl group of cyclodextrins, polycaprolactone (polyester) chain is introduced by performing ring-opening polymerization of ⁇ -caprolactone via the hydroxyl group of the hydroxypropyl group.
  • the polyrotaxane may be introduced into the terminal hydroxyl group of the caprolactone chain.
  • compatibility is improved.
  • polyrotaxane also causes a curing reaction, polyrotaxane is dispersed at the molecular level (nm order), and a transparent cured product is obtained.
  • the polyrotaxane does not have a curing reactive substituent, the polyrotaxane is dispersed on the order of ⁇ m, and an opaque cured product is obtained. That is, when used for applications requiring transparency, such as optical electronic materials, the polyrotaxane preferably has a curing reactive substituent.
  • curing reactive substituent examples include (meth) acryloyl group, vinyl group, allyl group and the like.
  • the “(meth) acryloyl” means at least one of “acryloyl” and “methacryloyl”.
  • the curing reactive substituent is a compound having a reactive group such as a hydroxyl group in the cyclic molecule before introducing the curing reactive substituent, a functional group capable of reacting with the reactive group, and a curing reactive substituent. It can introduce
  • a (meth) acryloyl group for example, (meth) acryloyl chloride, (meth) acrylic anhydride, 2 -(Meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ⁇ -methacryloyloxy- ⁇ -butyrolactone, ⁇ -methacryloyloxy- ⁇ -butyrolactone and the like.
  • a vinyl group for example, p-vinylbenzoic acid, p-vinylbenzoic acid chloride, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, vinyl chloroacetate and the like can be mentioned.
  • an allyl group for example, p-allylbenzoic acid, p-allylbenzoic acid chloride, allyl isocyanate, allyl isothiocyanate and the like can be mentioned.
  • (meth) acryloyl chloride, 2- (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, 3-isopropenyl isocyanate, ⁇ , ⁇ -Dimethylbenzyl, vinyl chloroacetate and allyl isocyanate are preferred.
  • the “(meth) acrylate” means at least one of “acrylate” and “methacrylate”.
  • the introduction rate of the curing reactive substituent is preferably a lower limit of 5 mol% and a preferable upper limit of 80 mol% with respect to the total hydroxyl groups of the cyclodextrins.
  • the introduction rate of the curing reactive substituent is within this range, the cured product is particularly excellent in transparency.
  • a more preferable lower limit of the introduction ratio of the curing reactive substituent is 10 mol%, and a more preferable upper limit is 50 mol%.
  • the preferable lower limit of the contact ratio is 0.1%, the preferable upper limit is 60%, the more preferable lower limit is 1%, the more preferable upper limit is 50%, the still more preferable lower limit is 5%, and the further preferable upper limit is 40%.
  • the maximum inclusion amount can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, the maximum inclusion amount when the linear molecule is polyethylene glycol and the cyclic molecule is ⁇ -cyclodextrin is experimentally determined (see Macromolecules 1993, 26, 5698-5703).
  • the linear molecule can be clasped into the opening of a cyclic molecule, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, polytetrahydrofuran.
  • a cyclic molecule for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, polytetrahydrofuran.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • casein gelatin, starch, cellulosic resin (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyolefin resin (polyethylene, polypropylene, polyisobutylene, and Copolymers of these with other olefinic monomers), polyester resins, polyvinyl chloride resins (vinyl chloride-vinyl acetate) Copolymer), polystyrene resin (polystyrene, acrylonitrile-styrene copolymer, etc.), acrylic resin (poly (meth) acrylic acid, polymethyl methacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate) Polymer), polycarbonate resin, polyurethane resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.), poly
  • polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether are preferable, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, Polyethylene and polypropylene are more preferred, and polyethylene glycol is even more preferred.
  • the “(meth) acryl” means at least one of “acryl” and “methacryl”.
  • the preferable lower limit of the weight average molecular weight of the linear molecule is 3000, and the preferable upper limit is 300,000.
  • the more preferable lower limit of the weight average molecular weight of the linear molecule is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 50,000.
  • the mass average molecular weight of the said linear molecule is a value calculated
  • Examples of the column for measuring the mass average molecular weight in terms of polyethylene glycol by GPC include TSKgel SuperAWM-H (manufactured by Tosoh Corporation). Further, the mass average molecular weight other than the linear molecule is a value determined by polystyrene conversion after measurement by GPC unless otherwise specified. Examples of the column for measuring the mass average molecular weight in terms of polystyrene by GPC include TSKgel SuperHM-M (manufactured by Tosoh Corporation).
  • the linear molecule is preferably polyethylene glycol
  • the cyclic molecule is preferably a molecule derived from ⁇ -cyclodextrin.
  • the blocking groups are arranged at both ends of the linear molecule included in the cyclic molecule and have a role of preventing the cyclic molecule from leaving.
  • a conventionally known method for example, a method described in JP-A-2005-154675
  • JP-A-2005-154675 a method described in JP-A-2005-154675
  • Examples of the blocking group include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, anthracenes, and the like, and a mass average molecular weight of 1,000 to 1,000,000. Examples include a main chain or a side chain of a polymer. Of these, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes are preferable, and adamantane groups and trityl groups are more preferable.
  • Examples of the polymer having a mass average molecular weight of 1,000 to 1,000,000 include polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylate. Two or more of these blocking groups may be mixed in the polyrotaxane.
  • the content of the polyrotaxane is such that a preferable lower limit is 1 part by mass and a preferable upper limit is 20 parts by mass with respect to 100 parts by mass of the maleimide compound.
  • a preferable lower limit is 1 part by mass
  • a preferable upper limit is 20 parts by mass with respect to 100 parts by mass of the maleimide compound.
  • the minimum with more preferable content of the said polyrotaxane is 3 mass parts, and a more preferable upper limit is 10 mass parts.
  • the minimum with preferable content of the said polyrotaxane in the whole thermosetting resin composition of this invention is 0.5 mass%, and a preferable upper limit is 10 mass%.
  • the minimum with more preferable content of the said polyrotaxane is 2 mass%, and a more preferable upper limit is 5 mass%.
  • thermosetting resin composition of the present invention further has, as a curing agent, an aromatic compound having two or more alkenyl groups in one molecule other than the maleimide compound, and two or more amino groups in one molecule. It is preferable to contain a compound and at least one compound selected from the group consisting of aromatic compounds each having one alkenyl group and one amino group in one molecule. These compounds have a role of promoting the formation of a three-dimensional network structure and further improving the heat resistance of the resulting cured product.
  • Examples of the aromatic compound having two or more alkenyl groups in one molecule include compounds represented by the following formula (5).
  • R 5 is a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms
  • s is an integer of 1 to 4
  • X is a monovalent atom or atomic group or a divalent or higher residual group.
  • a group, l is an integer of 1 or more, and when X does not include an alkenyl group, at least one of s and l is 2 or more, and when X is a monovalent atom or atomic group, l Is 1.
  • each R 5 may be the same or different.
  • examples of the monovalent atom or atomic group represented by X include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the like.
  • the divalent or higher valent residue represented by X is, for example, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N ⁇ N—, —N ⁇ C ⁇ N—.
  • a compound represented by the following formula (6) is preferable from the viewpoint of heat resistance of the cured product.
  • W represents a bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N ⁇ N—, —N ⁇ C ⁇ N—, —C ( ⁇ O) —, —SO 2 —, —S ( ⁇ O) —, —O—, —S—, a divalent substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a divalent substituted or unsubstituted aromatic hydrocarbon group
  • R 6 and R 7 are each independently a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms
  • t and u are each independently an integer of 0 to 4
  • t + u is 2 That's it.
  • the plurality of R 6 or R 7 may be the same or different.
  • aromatic compound having two or more alkenyl groups in one molecule examples include 2,2′-diallyl bisphenol A, 2,2′-diallyl bisphenol F, 2,2-bis [4 -Hydroxy-3,5-di (2-propenylphenyl)] propane, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfide Bis [4-hydroxy-3- (2-propenyl) phenyl] ether, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone, 1,1-bis [4-hydroxy-3- (2- Propenyl) phenyl] ethylbenzene, 1,1-bis [4-hydroxy-3- (2-propenyl) phenyl] cyclohexane, 1,1,1,3 3,3-hexafluoro-2,2-bis- [4-hydroxy-3- (2-prop
  • the compound having two or more amino groups in one molecule is preferably a compound represented by the following formula (7) from the viewpoint of heat resistance of the cured product.
  • V is a divalent substituted or unsubstituted aromatic hydrocarbon group or a divalent substituted or unsubstituted alicyclic hydrocarbon group.
  • the compound having two or more amino groups in one molecule include metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane, and 4,4′-diamino.
  • the alkenyl group of the aromatic compound having two or more alkenyl groups in one molecule and the amino group of the compound having two or more amino groups in one molecule are: It is preferable that the molecule exists at a position where the molecule has line symmetry.
  • Examples of the aromatic compound having one alkenyl group and one amino group in one molecule include 2-allylaniline, 2-allyl-5-methoxyaniline, 4-allylaniline, 4-isopropenylaniline, Examples include 2-methyl-4-isopropenylaniline, 3-methyl-4-isopropenylaniline, 3-chloro-4-isopropenylaniline, 4-isobutenylaniline and the like.
  • the preferred lower limit of the maleimide compound / curing agent is preferably 0.5, as the content ratio of the maleimide compound and the curing agent.
  • the upper limit is 5.
  • the maleimide compound / curing agent (molar ratio) is within this range, the resulting cured product is particularly excellent in heat resistance and flexibility.
  • the more preferable lower limit of the maleimide compound / curing agent (molar ratio) is 1, and the more preferable upper limit is 3.
  • curing agent in the whole thermosetting resin composition of this invention is 4.5 mass%, a preferable upper limit is 60 mass%, A more preferable minimum is 10 mass%, A more preferable upper limit Is 45% by weight.
  • thermosetting resin composition of the present invention is, as necessary, other resins, curing accelerators, reinforcing fiber materials, antioxidants, pigments (dyes), ultraviolet absorptions, as long as the object of the present invention is not impaired.
  • You may contain various additives, such as an agent, a flame retardant, and a coupling agent.
  • Examples of the other resin include rubber components such as natural rubber, butadiene rubber, nitrile rubber, and carboxy-modified nitrile rubber, polyolefin, acid-modified polyolefin, polyester, polyether, polyethersulfone, polyetheretherketone, and polyether.
  • examples thereof include thermoplastic resins such as imide, polysulfone, polyphenylene sulfide, and nylon.
  • curing accelerator examples include N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, dimethylaminomethylphenol, benzyldimethylamine, trisdimethylaminomethylphenol, 1,8-diazabicyclo [5,4,0].
  • the reinforcing fiber material examples include plant fibers such as paper, cotton, hemp, banana fiber, bamboo fiber and bagasse fiber, animal fibers such as silk and wool, glass fiber, ceramic fiber, carbon fiber, and silicon carbide fiber. And synthetic polymer fibers such as aramid fibers, polyester fibers, and nylon fibers. Examples of the form of these reinforcing fiber materials include nonwoven fabric, woven fabric, filament, strand, chopped strand, yarn, roving and the like.
  • antioxidants examples include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl- ⁇ - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2 - ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl] 2,4,8,10- Tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-buty
  • pigment (dye) examples include titanium oxide, zinc oxide, molybdenum red, cadmium yellow, cadmium red, bitumen, ultramarine blue, bengara, and carbon black.
  • Examples of the ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxy Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfo Benzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 '-G-tert Butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-
  • the flame retardant examples include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetra Bromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2, Brominated flame retardants such as 4,6-tris (tribromophenoxy) -1,3,5-triazine, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl
  • Examples of the coupling agent include 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane, and 3- (2-aminoethyl).
  • thermosetting resin composition of the present invention is obtained by uniformly dissolving the maleimide compound, the polyrotaxane, and additives such as a curing agent and a curing accelerator used as necessary in an organic solvent, and then adding the organic solvent. And a method of uniformly kneading using a melt mixing apparatus such as a roll or a kneader.
  • thermosetting resin composition of the present invention varies depending on the type of material used and the blending ratio, but usually, the curing reaction hardly proceeds at the melt mixing temperature or solution mixing temperature when producing the thermosetting resin composition.
  • the resulting thermosetting resin composition can be cured by further heating.
  • the curability when curing the thermosetting resin composition of the present invention varies depending on the presence or absence of a curing accelerator, the heating temperature, the way of heating, and the like, and the curing reaction is controlled by adjusting these conditions. be able to.
  • the curing temperature for curing the thermosetting resin composition of the present invention is usually 80 to 350 ° C., preferably 120 to 300 ° C., more preferably 150 to 250 ° C.
  • the curing time for curing the thermosetting resin composition of the present invention is usually 6 to 24 hours, preferably 6 to 12 hours.
  • a molding material obtained by blending a filler with the thermosetting resin composition of the present invention is also one aspect of the present invention.
  • functions such as high conductivity, high thermal conductivity, insulation, and low hygroscopicity can be improved, and a thermosetting resin composition suitable for the application can be obtained.
  • the filler inorganic fillers or organic fillers having various shapes can be used.
  • metal particles such as aluminum powder, iron powder, copper powder, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, clay, mica, talc, iron oxide, zinc oxide, titanium oxide,
  • Inorganic particles such as barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, alumina, glass, etc., wood powder, pulp powder, various textile pulverized products, pulverized products of thermosetting resin cured products, etc. Organic particles etc. are mentioned.
  • the minimum with preferable content of the said filler in the whole molding material of this invention is 1 mass%, and a preferable upper limit is 90 mass%.
  • a preferable upper limit is 90 mass%.
  • the minimum with more preferable content of the said filler is 5 mass%, and a more preferable upper limit is 80 mass%.
  • Examples of the method for producing the molding material of the present invention include a method of melt-kneading the thermosetting resin composition of the present invention and the filler.
  • a molded body obtained by curing the molding material of the present invention is also one aspect of the present invention.
  • a conventionally known method can be used as a method for obtaining the molded product of the present invention by curing the molding material of the present invention.
  • injection molding method, melt casting method, compression molding method, transfer molding method, prepreg lamination press molding method, prepreg autoclave molding method, matched die molding method, hand lay-up molding method, SMC (Sheet Molding Compound) examples thereof include a press molding method, a BMC (Bulk Molding Compound) molding method, a resin infusion molding method, a filament winding molding method, a pultrusion molding method, and a pin winding molding method.
  • thermosetting resin composition of the present invention can be formed into a prepreg by dissolving in a solvent and impregnating and drying the reinforcing fiber material as a varnish, a hand lay-up method, a spray-up method, or the like. it can.
  • thermosetting resin composition of the present invention can be used for electrical / electronic materials such as semiconductor encapsulating materials and printed circuit boards, automobile parts such as balance shaft gears, clutch facings, brake linings, disk pads, railway vehicles, aircraft, It can be used for structural materials, parts, interior / exterior materials, floor materials, wall materials, panels, etc. used in ships and the like. It can also be used for interior / exterior materials, ceiling materials, wall materials, heat insulation panels, refrigeration / freezer warehouse panels, etc. used in buildings. Furthermore, it can be applied to various pipe heat insulation materials for tanks and plants. In addition, it can also be applied to resin concrete, sports applications such as golf shafts and fishing rods, paints, and adhesives. Especially, since the hardened
  • thermosetting resin composition which can obtain the hardened
  • cured material, molding material, and molded object which use this thermosetting resin composition can be provided.
  • FIG. 6 is a graph showing the relationship between the loss elastic modulus E ′′ and temperature in the cured products obtained in Example 1, Example 2, and Comparative Example 1.
  • 6 is a graph showing the relationship between the loss tangent tan ⁇ and the temperature in the cured products obtained in Example 1, Example 2, and Comparative Example 1.
  • the obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol, stirred to reprecipitate, and the precipitate was taken out by a centrifugal separation method.
  • the obtained precipitate was dried to obtain 108.9 g of a polyrotaxane (hereinafter, also referred to as “MPR”) having a methacryloyloxyethylcarbamoyl group which is a curing reactive substituent in the cyclic molecule.
  • MPR polyrotaxane
  • Example 1 6.6 g of PR was dissolved in 3 times the amount of acetone, and this was added to 100 g of 2,2′-diallylbisphenol A heated to 90 ° C. Acetone was removed by vacuum degassing at 110 ° C. for 60 minutes. Next, 116.2 g of bis (4-maleimidophenyl) methane was added, heated and melted at 170 ° C., and vacuum degassed at 120 ° C. for 15 minutes to obtain a thermosetting resin composition.
  • thermosetting resin composition was cast into an aluminum plate mold using a Teflon (registered trademark) plate having a thickness of 3 mm as a spacer, and in order, 2 hours at 160 ° C., 2 hours at 180 ° C., 2 at 200 ° C.
  • the cured product was obtained by heating at 230 ° C. for 2 hours and at 250 ° C. for 2 hours.
  • Example 2 A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that the amount of PR was 11.0 g.
  • Example 3 A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that MPR 6.5 g was used instead of PR 6.6 g.
  • Example 4 A thermosetting resin composition and a cured product were obtained in the same manner as in Example 3 except that the blending amount of MPR was 10.9 g.
  • Example 5 Thermosetting resin composition and cured product in the same manner as in Example 1 except that 183 g of 4-methyl-1,3-phenylenebismaleimide was used instead of 116.2 g of bis (4-maleimidophenyl) methane. Got.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 5 except that 6.5 g of MPR was used instead of PR 6.6 g.
  • Example 7 PR5.8 g was dissolved in 3 times the amount of acetone, and this was heated to 170 ° C. 100 g of bis (4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide 50 g, 1,6-bismaleimide- A mixture of 16.7 g of (2,2,4-trimethyl) hexane was added, and vacuum deaeration was performed at 130 ° C. for 20 minutes to remove acetone. 25 g of metaphenylenediamine melted by heating was added thereto to obtain a thermosetting resin composition.
  • thermosetting resin composition was cast into an aluminum plate mold using a Teflon (registered trademark) plate having a thickness of 3 mm as a spacer, and in order, 2 hours at 160 ° C., 2 hours at 180 ° C., 2 at 200 ° C.
  • the cured product was obtained by heating at 230 ° C. for 2 hours and at 250 ° C. for 2 hours.
  • Example 8 A thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that MPR 5.8 g was used instead of PR 5.8 g.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that PR was not used.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 5 except that PR was not used.
  • thermosetting resin composition (Comparative Example 3) A thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that PR was not used.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that 6.6 g of PCL-PO- ⁇ -CD was used instead of PR.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that 11.0 g of PCL-PO- ⁇ -CD was used instead of PR.
  • thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that 5.8 g of PCL-PO- ⁇ -CD was used instead of 5.8 g of PR.
  • 1 to 3 are graphs showing the relationship between storage elastic modulus E ′ and temperature, loss elastic modulus E ′′, and cured products obtained in Example 1, Example 2, and Comparative Example 1, respectively. It is a graph which shows the relationship between temperature, and the graph which shows the relationship between loss tangent tan-delta and temperature.
  • thermolysis temperature For each cured product obtained in the examples and comparative examples, a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., “TG-DTA220”) was used at a temperature rising rate of 10 ° C./min. It heated in air atmosphere to 0 degreeC, and measured 5% weight loss temperature as thermal decomposition temperature.
  • thermosetting resin composition prepared by the method similar to an Example and a comparative example, the tensile shear bond strength was measured.
  • Oxygen-free copper JIS C1020P
  • Pretreatment of the test piece was performed by degreasing with acetone, polishing with No. 240 polishing paper, washing with running cold water, then warm water, and drying.
  • the prepared thermosetting resin composition was applied to a test piece and heated at 160 ° C. for 2 hours, at 180 ° C. for 2 hours, at 200 ° C. for 2 hours, at 230 ° C. for 2 hours, and at 250 ° C. for 2 hours.
  • a shear bond strength test piece was obtained.
  • Tensile shear adhesive strength was measured under a load speed of 5 mm / min according to JIS K-6850 using a universal material testing machine (manufactured by Minebea, “Technograph AL-50kNB”).
  • thermosetting resin composition which can obtain the hardened
  • cured material, molding material, and molded object which use this thermosetting resin composition can be provided.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne une composition de résine thermodurcissable qui peut donner des objets durcis excellents en ce qui concerne la ténacité et l'adhésivité, sans abaisser considérablement la résistance mécanique ou la résistance à la chaleur. La présente invention porte en outre sur un objet durci, sur un matériau de moulage et sur un objet moulé qui sont obtenus à partir de ou comprenant la composition de résine thermodurcissable. La composition de résine thermodurcissable de la présente invention comprend un composé présentant un groupe maléimide et un polyrotaxane qui comprend des molécules cycliques, une molécule linéaire traversant les cavités des molécules cycliques dans un état en biais et des groupes de blocage qui bloquent les deux extrémités de la molécule linéaire.
PCT/JP2017/008472 2016-04-27 2017-03-03 Composition de résine thermodurcissable, objet durci, matériau de moulage et objet moulé WO2017187783A1 (fr)

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WO2018124158A1 (fr) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Préimprégné, carte stratifiée, carte stratifiée plaquée de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
WO2019131574A1 (fr) * 2017-12-27 2019-07-04 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié, stratifié plaqué d'une feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
JP2021095542A (ja) * 2019-12-19 2021-06-24 株式会社ダイセル 硬化性組成物
EP3845567A4 (fr) * 2018-08-27 2022-05-04 ASM Inc. Polyrotaxane, composition thermodurcissable comprenant ledit polyrotaxane, objet réticulé thermodurci, procédé de production de polyrotaxane et procédé de production d'un objet réticulé thermodurci

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WO2018124158A1 (fr) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Préimprégné, carte stratifiée, carte stratifiée plaquée de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
JP6424992B1 (ja) * 2016-12-28 2018-11-21 三菱瓦斯化学株式会社 プリプレグ、積層板、金属箔張積層板、プリント配線板、及び多層プリント配線板
JP2019048990A (ja) * 2016-12-28 2019-03-28 三菱瓦斯化学株式会社 プリプレグ、積層板、金属箔張積層板、プリント配線板、及び多層プリント配線板
WO2019131574A1 (fr) * 2017-12-27 2019-07-04 三菱瓦斯化学株式会社 Composition de résine, préimprégné, stratifié, stratifié plaqué d'une feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche
JPWO2019131574A1 (ja) * 2017-12-27 2019-12-26 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、積層板、金属箔張積層板、プリント配線板及び多層プリント配線板
KR20200044975A (ko) * 2017-12-27 2020-04-29 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 프리프레그, 적층판, 금속박 피복 적층판, 프린트 배선판 및 다층 프린트 배선판
JP2020117714A (ja) * 2017-12-27 2020-08-06 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、積層板、金属箔張積層板、プリント配線板及び多層プリント配線板
KR102199879B1 (ko) 2017-12-27 2021-01-07 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 프리프레그, 적층판, 금속박 피복 적층판, 프린트 배선판 및 다층 프린트 배선판
JP7269537B2 (ja) 2017-12-27 2023-05-09 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、積層板、金属箔張積層板、プリント配線板及び多層プリント配線板
EP3845567A4 (fr) * 2018-08-27 2022-05-04 ASM Inc. Polyrotaxane, composition thermodurcissable comprenant ledit polyrotaxane, objet réticulé thermodurci, procédé de production de polyrotaxane et procédé de production d'un objet réticulé thermodurci
US12006402B2 (en) 2018-08-27 2024-06-11 Asm Inc. Polyrotaxane, thermally curable composition including said polyrotaxane, thermally cured crosslinked object, production method for polyrotaxane, and production method for thermally cured crosslinked object
JP2021095542A (ja) * 2019-12-19 2021-06-24 株式会社ダイセル 硬化性組成物

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