WO2015163182A1 - Polymère, composition, produit durci, adhésif en forme de film, et stratifié - Google Patents

Polymère, composition, produit durci, adhésif en forme de film, et stratifié Download PDF

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WO2015163182A1
WO2015163182A1 PCT/JP2015/061406 JP2015061406W WO2015163182A1 WO 2015163182 A1 WO2015163182 A1 WO 2015163182A1 JP 2015061406 W JP2015061406 W JP 2015061406W WO 2015163182 A1 WO2015163182 A1 WO 2015163182A1
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group
polymer
formula
composition
cured product
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PCT/JP2015/061406
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Japanese (ja)
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岩沢　晴生
高明 宇野
太郎 内田
晋太郎 藤冨
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Jsr株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a polymer, a composition, a cured product, a film adhesive, and a laminate.
  • Fiber reinforced plastic (FRP) made from fiber and matrix resin has great merit due to its weight reduction, and is used in parts such as ships, automobiles, aircraft, and sporting goods.
  • a matrix resin an epoxy resin or a vinyl group-containing resin having excellent adhesive strength with fibers and metals and excellent heat resistance is used (Patent Documents 1 and 2).
  • an epoxy resin used for a matrix resin of a fiber reinforced plastic is required to be a polymer that forms a cured product having excellent heat resistance and excellent adhesive strength.
  • An object of the present invention is to provide a polymer that forms a cured product excellent in heat resistance and adhesive strength, a composition containing the polymer, and a cured product obtained by curing these. .
  • the present invention provides the following [1] to [8].
  • [1] A polymer having a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2).
  • R 1 and R 3 each represent a group bonded to the naphthalene ring via an oxygen atom, a group having an epoxy group or an ethylenically unsaturated group, or —CH a group represented by 2 oR 5 .
  • R 5 is a hydrogen atom
  • .R 1 and R 3 represents an alkyl group or an acetyl group having 1 to 10 carbon atoms, each, when there are a plurality, R 1 together and R 3 may be the same as or different from each other
  • R 2 and R 4 each represent a group bonded to the naphthalene ring and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
  • a and c each represent an integer of 1 to 6
  • b and d represents an integer of 0 to 5
  • a + b 6
  • c + d 6
  • m and n each represents an integer of 2 or more.
  • R 1 and m are the same as R 1 and m in the formula (1), respectively.
  • a composition comprising the polymer according to any one of [1] to [3] and a solvent.
  • a cured product obtained by curing the polymer according to any one of [1] to [3].
  • a cured product obtained by curing the composition according to any of [4] or [5].
  • a film adhesive obtained by impregnating at least a fiber with the composition according to the above [4] or [5] and semi-curing the fiber.
  • a laminate obtained by laminating a layered member via the film adhesive according to [8].
  • the polymer of the present invention and the composition containing the polymer are cured with excellent heat resistance and excellent adhesive strength.
  • FIG. 1 is an infrared spectrum of the polymer (a1) synthesized in the example.
  • polymer (A) has a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2). .
  • R 1 and R 3 each represent a group bonded to the naphthalene ring via an oxygen atom, a group having an epoxy group or an ethylenically unsaturated group, or —CH a group represented by 2 oR 5 .
  • R 5 is a hydrogen atom
  • .R 1 and R 3 represents an alkyl group or an acetyl group having 1 to 10 carbon atoms, each, when there are a plurality, R 1 together and R 3 may be the same as or different from each other
  • R 2 and R 4 each represent a group bonded to the naphthalene ring and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
  • the polymer (A) has a polynaphthylene structure.
  • the polymerization bond position in the structural unit represented by the formula (1) and the formula (2) is not limited.
  • R 1 and R 3 are groups bonded to the naphthalene ring through an oxygen atom, and the bonding position is not limited.
  • R 2 and R 4 are groups bonded to the naphthalene ring, and the bonding positions are not limited.
  • Examples of the group having an epoxy group represented by R 1 and R 3 include an epoxy group, a glycidyl group, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group; 3,4-epoxycyclohexylmethyl.
  • Examples of the group having an ethylenically unsaturated group represented by R 1 and R 3 include a vinyl group, an allyl group, a styryl group, a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, and a (meth) acryloyl group.
  • Examples include oxypropyl, vinylphenyl group, vinylbenzyl, styrylmethyl group, and styrylethyl group.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R 5 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, Examples include hexyl group, octyl group, decyl group, dodecyl group, and hexadecanyl group.
  • Examples of the halogen atom represented by R 2 and R 4 include a chloro group, a bromo group, and a fluoro group.
  • the polymer (A) may contain structural units other than the structural units represented by the formula (1) and the formula (2).
  • Examples of the structural unit other than the structural units represented by the formula (1) and the formula (2) include structural units derived from other monomers described later.
  • the total content (mol%) of the structural units represented by the formula (1) and the formula (2) contained in the polymer (A) is determined from the viewpoint of the heat resistance and adhesive strength of the cured product. It is usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more with respect to the total of all structural units contained in A).
  • the total content (% by mass) of the structural units represented by the formula (1) and the formula (2) contained in the polymer (A) is heavy from the viewpoint of heat resistance and adhesive strength of the cured product.
  • the amount is usually 60% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total of all the structural units contained in the coalescence (A).
  • the said structural unit shows the structural unit derived from the monomer used for the synthesis
  • the proportion of the structural units of the formula (1) and the formula (2) in all the structural units of the polymer (A) can be calculated from the integral value of 1 H-NMR.
  • the polymer (A) preferably contains a structural unit represented by the formula (1) from the viewpoints of heat resistance and adhesive strength of the cured product.
  • the content (mol%) of the structural unit represented by the formula (1) contained in the polymer (A) is contained in the polymer (A) from the viewpoints of heat resistance and adhesive strength of the cured product.
  • it is 70 mol% or more with respect to the sum total of all the structural units, More preferably, it is 90 mol% or more, More preferably, it is 99 mol% or more.
  • the content rate (mass%) of the structural unit represented by the formula (1) contained in the polymer (A) is in the polymer (A) from the viewpoint of heat resistance and adhesive strength of the cured product.
  • the structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (3) from the viewpoint of heat resistance and adhesive strength of the cured product.
  • R 1 and m are the same as R 1 and m in the formula (1)).
  • the content (mol%) of the structural unit represented by the formula (3) contained in the polymer (A) is contained in the polymer (A) from the viewpoint of the heat resistance and adhesive strength of the cured product.
  • it is 70 mol% or more with respect to the sum total of all the structural units, More preferably, it is 90 mol% or more, More preferably, it is 99 mol% or more.
  • the content (mass%) of the structural unit represented by the formula (3) contained in the polymer (A) is in the polymer (A) from the viewpoint of heat resistance and adhesive strength of the cured product.
  • it is 80 mass% or more with respect to the sum total of all the structural units contained, More preferably, it is 90 mass% or more, More preferably, it is 99 mass% or more.
  • the weight average molecular weight of the polymer (A) calculated by gel permeation chromatography is usually 1,000 to 100,000.
  • the weight average molecular weight is a value calculated by the method described in the examples.
  • a polymer (A) can also be used independently, and can also be used as a composition mentioned later or hardened
  • the polymer of the present invention can be synthesized by combining known methods. For example, it can be synthesized by the method shown in the synthesis route shown in the following formula (4). Polynaphthylene having a phenolic hydroxyl group (hereinafter also referred to as “hydroxypolynaphthylene”) by a coupling reaction using a naphthalene derivative having a phenolic hydroxyl group as a monomer and other copolymerizable monomers as necessary. ) Is synthesized (hereinafter also referred to as “step 1”).
  • Step 2 the hydroxypolynaphthylene is reacted with a halide having an ethylenically unsaturated group to synthesize a polynaphthylene having an ethylenically unsaturated group.
  • step 3 the ethylenically unsaturated group of the polynaphthylene having the ethylenically unsaturated group is oxidized to synthesize a polynaphthylene having an epoxy group (hereinafter also referred to as “step 3”).
  • R 5 represents a group having an ethylenically unsaturated bond group.
  • R 6 represents a group having an epoxy group.
  • R 2 , a, b and m are each in the formula (1). (Same as these symbols.)
  • the polymer (A) in which R 1 and R 3 in the formula (1) are groups having an ethylenically unsaturated bond group can be synthesized by performing up to the step 2, and the formula (1)
  • the polymer (A) in which R 1 and R 3 are groups having an epoxy group can be synthesized by performing up to the step 3.
  • Step 1 is a step of synthesizing polynaphthylene having a phenolic hydroxyl group by a coupling reaction using a naphthalene derivative having a phenolic hydroxyl group as a monomer, together with another copolymerizable monomer as necessary.
  • naphthalene derivative having a phenolic hydroxyl group examples include 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-methyl-1-hydroxynaphthalene, 6-phenyl-2-hydroxynaphthalene, 1,3-dihydroxynaphthalene, , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, and 3-methyl-2,6- Dihydroxynaphthalene is mentioned.
  • the said naphthalene derivative which has a phenolic hydroxyl group may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the other copolymerizable monomers include phenol, p-isopropenylphenol, ethynylstyrene, propargylic acid, 6-hexynoic acid, 2-propyn-1-ol, and 1-butyn-3-ol. , 3-butyn-3-ol, 1-pentyn-3-ol, 4-pentyn-1-ol, 3-ethynylaniline, 4-ethynylaniline, and phenylacetylene.
  • the other copolymerizable monomers may be used alone or in combination of two or more.
  • the coupling reaction examples include a coupling reaction using a one-electron oxidizing agent.
  • the coupling reaction involves dissolving the naphthalene derivative having the phenolic hydroxyl group in a reaction solvent, and oxygen in the presence of a catalyst. This can be done by supplying
  • the reaction conditions in the coupling reaction using the one-electron oxidizing agent are usually 10 ° C. to 100 ° C. and 0.1 to 10 hours, and the type of catalyst, the naphthalene derivative, and the other copolymerization are possible. It is appropriately adjusted depending on the kind of the monomer.
  • Examples of the one-electron oxidizing agent include silver carbonate (Fetizon reagent), di- ⁇ -hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride, di- ⁇ .
  • the amount of the one-electron oxidant to be used is usually 0.0001 to 10 mol with respect to 1 mol of the naphthalene derivative having a phenolic hydroxyl group.
  • the reaction solvent in the coupling reaction using a one-electron oxidizing agent the naphthalene derivative having the phenolic hydroxyl group, the other copolymerizable monomer, the one-electron oxidizing agent, and the phenolic obtained by the coupling reaction
  • Any polynaphthylene having a hydroxyl group may be used, for example, methanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, ethyl lactate, lactic acid propane, butyl lactate, N, N-dimethylformamide is mentioned.
  • the reaction solution contains impurities other than polynaphthylene having a phenolic hydroxyl group such as a catalyst residue. For this reason, after completion
  • Step 2 is a step of synthesizing a polynaphthylene having an ethylenically unsaturated group by reacting the hydroxypolynaphthylene synthesized in the step 1 with a halide having an ethylenically unsaturated group.
  • Examples of the halide having an ethylenically unsaturated group include allyl chloride, allyl bromide, 4-chloro-1-butene, 3-chloro-1-butene, 1-chloro-3-methyl-2-butene, Examples include chloromethyl acrylate, chloromethyl methacrylate, chloroethyl acrylate, and chloroethyl methacrylate.
  • the halide having an ethylenically unsaturated group may be used alone or in combination of two or more.
  • the amount of the halide having an ethylenically unsaturated group is usually 1 to 5 mol with respect to 1 mol of the phenolic hydroxyl group of the naphthalene derivative converted to the ethylenically unsaturated group.
  • the reaction in Step 2 is usually carried out after converting the phenolic hydroxyl group of the naphthalene derivative having a phenolic hydroxyl group to an alkali metal salt using an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide.
  • an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide.
  • the amount of the alkali metal hydroxide used is usually 1 to 5 mol per 1 mol of the phenolic hydroxyl group of the naphthalene derivative converted to an ethylenically unsaturated group.
  • the reaction in Step 2 is usually carried out using a polar solvent such as n-propanol, 2-propanol, n-butanol, acetone, methyl ethyl ketone, dimethyl sulfoxide, N, N-dimethylformamide as a reaction solvent.
  • a polar solvent such as n-propanol, 2-propanol, n-butanol, acetone, methyl ethyl ketone, dimethyl sulfoxide, N, N-dimethylformamide
  • the reaction conditions in the reaction of Step 2 are usually 10 ° C. to 100 ° C. and 0.1 to 10 hours.
  • Step 3 The step 3 is a step of oxidizing the ethylenically unsaturated group of the polynaphthylene having an ethylenically unsaturated group synthesized in the step 2 to synthesize a polynaphthylene having an epoxy group.
  • the oxidation is usually performed using an oxidizing agent in a reaction solvent.
  • the oxidizing agent include nitric acid, m-chloroperbenzoic acid, peracetic acid, and performic acid.
  • reaction solvent examples include alcohols such as methanol, ethanol and propanol; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and cyclohexane; halogens such as chloroform; and aromatic carbonization such as benzene and toluene. Hydrogen is mentioned.
  • the oxidation may be performed in a two-layer system of water and an organic solvent layer using a phase transfer catalyst such as a quaternary ammonium salt.
  • a phase transfer catalyst such as a quaternary ammonium salt.
  • the conditions for the oxidation are usually 10 ° C. to 100 ° C. and 2 to 40 hours.
  • the reaction solution contains impurities other than polynaphthylene having an epoxy group such as a catalyst residue.
  • a well-known purification method for example, a reprecipitation method and a liquid washing method.
  • solvent (B) examples include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether.
  • ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate
  • propylene glycol such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether.
  • Monoalkyl ethers propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as butyl cellosolve; Carbitols such as bitol; Lactic acid esters such as ethyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, isopropyl acetate, n-butyl propionate, isobutyl propionate; Methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl propionate, methyl pyruvate, ethyl pyruvate; ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-h
  • ketones, ethers, and alcohols are preferable because the polymer (A) can be uniformly dissolved.
  • Solvent (B) may be used alone or in combination of two or more.
  • the amount of the solvent (B) used is usually such an amount that the solid content concentration of the composition is 1 to 90% by mass, and is appropriately adjusted depending on the purpose and use of the composition.
  • Curing accelerator (C) is for the purpose of accelerating the crosslinking reaction of the group having an epoxy group or the group having an ethylenically unsaturated double bond, which is a crosslinkable group of the polymer (A), and accelerates the curing rate.
  • a curing accelerator used in a normal crosslinking reaction can be used.
  • examples of the curing accelerator (C) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, anhydrous Acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride; diethylammonium triflate, triethylammonium triflate, Trifluorate salts such as diisopropylammonium triflate and ethyl isopropylammonium triflate; Boron compounds such as metal fluoroboron complex and boron trifluoride complex; Bis (perfluoroalkylsulfonyl) methane metal salt; PCl 5
  • examples of the curing accelerator (C) include IRGACURE127, 184, 369, 651, 754, 907, 2959, OXE01, and OXE02 (trade name) manufactured by BASF, pentafluorophenyl borate toluylcumyl iodonium salt, Sun-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110L, SI-145, SI-145, SI-150, SI-160, SI-110L, and SI-180L Radical polymerization initiators such as (Sanshin Chemical Industry Co., Ltd., product name).
  • One type of curing accelerator (C) may be used alone, or two or more types may be used in combination.
  • the content of the curing accelerator (C) is usually 0.5 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the crosslinking agent (B). is there.
  • content of a hardening accelerator (C) is the said range, the hardened
  • Crosslinking agent (D) The crosslinking agent (D) is used for the purpose of adjusting the curing rate of the composition or for the purpose of improving the adhesive strength.
  • the crosslinking agent (D) may be any compound that undergoes a crosslinking reaction by heat.
  • a compound having an epoxy group hereinafter also referred to as “epoxy crosslinking agent”
  • a benzoxazine ring-containing compound hereinafter referred to as “benzoxazine”.
  • a compound having active methylene hereinafter also referred to as “active methylene crosslinking agent”
  • oxetane crosslinking agent a compound having an isocyanate group
  • crosslinking agent a compound having an isocyanate group
  • oxazoline ring-containing compound hereinafter, also referred to as “oxazoline cross-linking agent”.
  • These crosslinking agents may be low molecular weight or high molecular weight.
  • the said epoxy crosslinking agent shows the compound which has an epoxy group except the said polymer (A).
  • epoxy crosslinking agent examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy.
  • Resin phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, cycloaliphatic epoxy resin, aliphatic epoxy resin epoxy resin; resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol Polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene Glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, epoxy compounds such as trimethylolpropane triglycidyl ether; and the like.
  • benzoxazine crosslinking agent examples include compounds described in JP-A-2006-335671, JP-A-2008-195907, JP-A-2012-036318, and JP-A-2009-001755.
  • Examples of the active methylene crosslinking agent include compounds described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297.
  • melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5,5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetrao
  • oxetane crosslinking agent examples include compounds described in JP 2010-197996 A. Specifically, 1,4-bis ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ benzene (trade name “OXT-121”, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- ⁇ [ (3-Ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane (trade name “OXT-221”, manufactured by Toagosei Co., Ltd.), 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (Trade name “ETERRNACOLL OXBP” manufactured by Ube Industries), bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phen
  • isocyanate crosslinking agent examples include compounds described in JP-A-2005-298724 and JP-A-2012-128099. Specific examples include tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.
  • oxazoline crosslinking agent examples include 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), and 2,2′-bis (4-ethyl-2-).
  • Oxazoline 2,2'-bis (5-methyl-2-oxazoline), 2,2'-bis (4,4-dimethyl-2-oxazoline), 2,2'-bis (5,5-diethyl-) 2-oxazoline), 2,2′-bis (4-propyl-2-oxazoline), 2,2′-bis (4-phenyl-2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ) Ethane, 1,2-bis (4-methyl-2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,4-bis (4,4-dimethyl) -2-oxazolin-2-yl) cyclohexane, , 3-bis (2-
  • an epoxy crosslinking agent is preferable from the viewpoint of adhesive strength, and among the epoxy crosslinking agents, a bisphenol type epoxy resin is preferable.
  • crosslinking agent (D) one type may be used alone, or two or more types may be used in combination.
  • the content of the crosslinking agent (D) is usually 10 to 2000 parts by mass, preferably 100 to 1500 parts by mass, more preferably 150 to 1000 parts by mass with respect to 100 parts by mass of the polymer (A).
  • the usage-amount of a crosslinking agent (D) is the said range, the hardened
  • Other components include, for example, ⁇ -methacryloxypropyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate, and 1,2, Adhesion aids such as 3-benzotriazole; flame retardants such as phosphazene compounds and bromides to improve the flame retardancy of cured products; rubbers, rubber particles, etc. for imparting flexibility to the cured products Elasticity imparting agent; inorganic particles such as silica and titanium oxide; colorants such as dyes and pigments for imparting color to the cured product; fibers such as carbon fiber, glass fiber and synthetic resin fiber; polyethylene, polystyrene, And thermoplastic resins such as polyurethane.
  • Adhesion aids such as 3-benzotriazole
  • flame retardants such as phosphazene compounds and bromides to improve the flame retardancy of cured products
  • rubbers, rubber particles, etc. for imparting flexibility to the cured products
  • composition of the present invention comprises the polymer (A) and the solvent (B) as essential components, and if necessary, the curing accelerator (C) and the crosslinking agent ( It can be produced by mixing D) and the other components. Moreover, you may remove the dust contained in a composition with a filter etc. after mixing.
  • Cured Product The cured product of the present invention is a cured product obtained by heat curing the polymer of the present invention or the composition of the present invention.
  • the cured product of the present invention can be used, for example, as a matrix for FRP.
  • the curing conditions of the cured product of the present invention are usually 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 250 ° C., and 0.1 to 10 hours, preferably 0.5 to 5 hours. Prior to the heat curing, heating may be performed at a temperature lower than 50 ° C. as preliminary curing.
  • Film adhesive The film adhesive of the present invention is a film obtained by thermosetting the thermosetting resin composition of the present invention so that the degree of curing is in a semi-cured state (B stage). Semi-cured product. Alternatively, a semi-cured product can be produced by impregnating a thermosetting resin composition into fibers such as non-woven cloth.
  • the curing conditions are usually 50 ° C.
  • the film adhesive of this invention can also be manufactured by thermosetting the thermosetting resin composition of this invention on a peeling film.
  • the laminate of the present invention is a laminate including the film adhesive of the present invention.
  • the laminate of the present invention is produced by, for example, laminating and curing other layered members such as metal members and fiber reinforced plastics through the film adhesive of the present invention. Since the laminate of the present invention uses the thermosetting resin composition of the present invention, the laminate has characteristics of high shear strength and difficulty in delamination.
  • the laminate of the present invention has the properties of high shear strength and resistance to delamination, it can be suitably used for ships, automobiles, aircraft, building materials, sports equipment, and the like.
  • the polymer was dissolved in 2-methylethanol to prepare a solution having a solid concentration of 20% by mass.
  • the solution was applied onto a substrate made of polyethylene terephthalate by a doctor blade method, and heated at 70 ° C. for 30 minutes and at 120 ° C. for 30 minutes to obtain a coating film.
  • the coating film was peeled off from the substrate, fixed to a metal frame with an adhesive tape, and then vacuum dried at 120 ° C. for 2 hours to obtain an infrared evaluation film having a thickness of 20 ⁇ m. This infrared evaluation film was subjected to infrared spectroscopic analysis with an infrared spectroscope.
  • the weight average molecular weight of the polymer (a1) was 48,000. An infrared spectrum of the polymer (a1) is shown in FIG. [Example 1] Synthesis of polymer (A1) Sodium hydroxide (3.80 g) was dissolved in water (250 g) in a flask to prepare a sodium hydroxide solution. Polymer (a1) (6.00 g) was added to an aqueous sodium hydroxide solution, and the mixture was stirred at 25 ° C. While stirring at 25 ° C., a solution of allyl bromide (13.8 g) dissolved in ethanol (30 ml) was dropped into the flask over 30 minutes, and then stirred at 25 ° C. for 12 hours. The solid precipitated in the flask was filtered off, and the residue was washed with water and vacuum dried at 50 ° C. to obtain a powdery polymer (A1). The results of 1 H-NMR measurement of the polymer (A1) are shown below.
  • the polymer (D4) (Mw: 5,000) was obtained by removing with a distiller.
  • the polymer (D4) was a polymer composed of 95 mol% of structural units represented by the following formula (d4) and 5 mol% of structural units represented by the following formula (d4 ′).
  • Examples 5 to 7, Comparative Example 1 A composition was prepared in the same manner as in Example 4 except that the types and amounts of the ingredients were changed as shown in Table 1. A cured product was produced using the obtained composition, and predetermined evaluation was performed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problème] L'invention a pour objectif de fournir un polymère qui forme un produit durci présentant une exceptionnelle résistance à la chaleur et une exceptionnelle résistance adhésive. [Solution] Le polymère selon l'invention présente une structure polynaphthylène contenant au moins un type de motif structural choisi entre la formule (1) et la formule (2). (Dans la formule (1) et la formule (2), R1 et R3 représentent chacun un groupe qui se lie à un cycle naphtalène par l'intermédiaire d'un atome d'oxygène ; c'est-à-dire un groupe comportant un groupe époxy ou un groupe à insaturation éthylénique, ou un groupe représenté par -CH2OR5. R5 représente un atome d'hydrogène, un groupe alkyle en C1-10, ou un groupe acétyle. Lorsque plusieurs R1 et R3 sont présents, chaque R1 et chaque R3 peuvent être identiques ou différents les uns des autres. R2 et R4 représentent chacun un groupe qui se lie à un cycle naphtalène ; c'est-à-dire un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle en C1-20. Lorsque plusieurs R2 et R4 sont présents, chaque R2 et chaque R4 peuvent être identiques ou différents les uns des autres. a et c représentent chacun un nombre entier de 2 à 6, b et d représentent chacun un nombre entier de 0 à 4, a + b = 6, et c + d = 6. m et n représentent chacun un nombre entier supérieur ou égal à 2.)
PCT/JP2015/061406 2014-04-23 2015-04-14 Polymère, composition, produit durci, adhésif en forme de film, et stratifié WO2015163182A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10886119B2 (en) 2018-08-17 2021-01-05 Rohm And Haas Electronic Materials Llc Aromatic underlayer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339347A (ja) * 1992-06-09 1993-12-21 Nippon Kayaku Co Ltd ポリフェノール樹脂、ポリフェノールエポキシ樹脂及びその製造法
JP2006291125A (ja) * 2005-04-14 2006-10-26 Hitachi Ltd 新規共重合体、樹脂組成物、その硬化物及び電子部品
JP2010090216A (ja) * 2008-10-06 2010-04-22 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
WO2014136773A1 (fr) * 2013-03-06 2014-09-12 Dic株式会社 Composition de résine époxy, produit durci, matière de rayonnement thermique et élément électronique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339347A (ja) * 1992-06-09 1993-12-21 Nippon Kayaku Co Ltd ポリフェノール樹脂、ポリフェノールエポキシ樹脂及びその製造法
JP2006291125A (ja) * 2005-04-14 2006-10-26 Hitachi Ltd 新規共重合体、樹脂組成物、その硬化物及び電子部品
JP2010090216A (ja) * 2008-10-06 2010-04-22 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
WO2014136773A1 (fr) * 2013-03-06 2014-09-12 Dic株式会社 Composition de résine époxy, produit durci, matière de rayonnement thermique et élément électronique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10886119B2 (en) 2018-08-17 2021-01-05 Rohm And Haas Electronic Materials Llc Aromatic underlayer

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