WO2016093254A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- WO2016093254A1 WO2016093254A1 PCT/JP2015/084451 JP2015084451W WO2016093254A1 WO 2016093254 A1 WO2016093254 A1 WO 2016093254A1 JP 2015084451 W JP2015084451 W JP 2015084451W WO 2016093254 A1 WO2016093254 A1 WO 2016093254A1
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- 0 CC(*)N1C=NC=C(C)C1 Chemical compound CC(*)N1C=NC=C(C)C1 0.000 description 2
- HLJDXGSNNOEKJD-UHFFFAOYSA-N CC(CC(O)=O)[n]1cncc1 Chemical compound CC(CC(O)=O)[n]1cncc1 HLJDXGSNNOEKJD-UHFFFAOYSA-N 0.000 description 1
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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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- 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
- C08G59/40—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 curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
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- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/52—Amino carboxylic acids
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- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- the present invention relates to a curable composition containing (A) an epoxy compound and (B) an imidazole compound having a specific structure, an adhesive comprising the curable composition, and a fiber-reinforced composite using the curable composition.
- the present invention relates to a material production method, and a fiber-reinforced composite material including a matrix made of a cured product of the curable composition and reinforcing fibers.
- a curable composition containing an epoxy compound and a curing agent or a curing catalyst is widely used in various applications such as adhesives, sealing of various electronic components, and matrix forming of fiber reinforced composite materials. .
- curable composition containing an epoxy compound used for such applications examples include (A) tetraglycidylamine type epoxy compound, (B) dicyandiamide, (C) diaminodiphenylsulfone, and (D) urea compound. And a curable composition having a viscosity within a specific range at 40 ° C. and a curing start temperature has been proposed (see Patent Document 1).
- the type of epoxy compound to be blended in the curable composition is usually selected from a wide range of options in consideration of various properties such as transparency, mechanical properties, and chemical resistance of the cured product.
- the curable composition described in Patent Document 1 is also problematic in that the choice of epoxy compound is limited to a very narrow range of tetraglycidylamine type epoxy compounds.
- the present invention has been made in view of the above problems, and provides a curable composition having a long pot life that can be cured at a low temperature and in a short time regardless of the type of epoxy compound to be blended.
- the purpose is to provide materials.
- this invention aims at providing the hardening
- the present inventors include (A) an epoxy compound and (B) an imidazole compound having a specific structure in a curable composition, and (B) an imidazole compound having a specific structure, and (C) a polyvalent amine.
- A an epoxy compound and (B) an imidazole compound having a specific structure in a curable composition
- B an imidazole compound having a specific structure
- C a polyvalent amine.
- the first aspect of the present invention is a curable composition containing (A) an epoxy compound and (B) an imidazole compound represented by the following formula (1).
- R 1 is a hydrogen atom or an alkyl group
- R 2 is an aromatic group that may have a substituent
- R 3 is an alkylene group that may have a substituent.
- R 4 are each independently a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, or organic group, n Is an integer from 0 to 3.
- the second aspect of the present invention is an adhesive comprising the curable composition according to the first aspect.
- the third aspect of the present invention is a method for producing a fiber-reinforced composite material, wherein the curable composition according to the first aspect impregnated in reinforcing fibers is cured by heating.
- the fourth aspect of the present invention is a fiber-reinforced composite material comprising a matrix made of a cured product of the curable composition according to the first aspect and reinforcing fibers.
- R 1 is a hydrogen atom or an alkyl group
- R 2 is an aromatic group that may have a substituent
- R 3 is an alkylene group that may have a substituent.
- R 4 are each independently a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, or organic group, n Is an integer from 0 to 3.
- the present invention it is possible to cure at a low temperature and in a short time regardless of the type of epoxy compound to be blended, and to provide a curable composition having a long pot life, and an adhesive comprising the curable composition , Providing a method for producing a fiber-reinforced composite material using the curable composition, and providing a fiber-reinforced composite material including a matrix made of the curable composition.
- curing agent mixed composition which can be hardened
- the curable compound includes (A) an epoxy compound and (B) an imidazole compound represented by the following formula (1) (hereinafter also referred to as (B) an imidazole compound).
- the curing reaction of the (A) epoxy compound is remarkably accelerated even at a low temperature of about 100 to 160 ° C., for example. .
- this curable composition gives the hardened
- R 1 is a hydrogen atom or an alkyl group
- R 2 is an aromatic group that may have a substituent
- R 3 is an alkylene group that may have a substituent.
- R 4 are each independently a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, or organic group, n Is an integer from 0 to 3.
- the curable composition further comprises (C) at least one cross-linking agent selected from the group consisting of a polyvalent amine compound and a polyvalent carboxylic acid anhydride, and (D) a curing agent for the purpose of further promoting the curing reaction.
- An accelerator may be included.
- the curable composition may contain a (S) solvent for the purpose of adjusting the viscosity and the coating property.
- S a (S) solvent
- essential or optional components contained in the curable composition will be described in order.
- An epoxy compound will not be specifically limited if it is a compound which has an epoxy group.
- An epoxy compound can be selected from the various compounds which have the epoxy group conventionally mix
- the epoxy compound may be a low molecular compound having an epoxy group which is a non-polymer, or may be a polymer having an epoxy group.
- a non-polymer having an epoxy group and a polymer having an epoxy group will be described in order.
- Non-polymer having epoxy group an aliphatic epoxy compound containing no aromatic group is preferable because a cured product formed using the curable composition is excellent in mechanical properties.
- an aliphatic epoxy compound having an alicyclic epoxy group is preferable because it provides a cured product having excellent transparency and hardness.
- aliphatic epoxy compound having an alicyclic epoxy group examples include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ⁇ -caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, ⁇ -methyl- ⁇ -Valerolactone modification , 4-epoxy
- alicyclic epoxy compounds represented by the following formulas (A1) to (A4) are preferable because they are excellent in transparency and give a hardened product.
- the alicyclic epoxy compounds represented by the following formulas (A1) to (A2) are more preferable.
- These alicyclic epoxy compounds may be used alone or in combination of two or more.
- Z represents a single bond, —O—, —O—CO—, —S—, —SO—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, — A divalent group selected from the group consisting of CBr 2 —, —C (CBr 3 ) 2 —, —C (CF 3 ) 2 —, and —R a19 —O—CO—, wherein R a19 is a carbon atom
- An alkylene group of formula 1 to 8, and R a1 to R a18 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
- R a19 is an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group or an ethylene group.
- R a1 to R a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R a2 and R a10 may be bonded to each other. Good.
- R a1 to R a10 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R a2 and R a8 may be bonded to each other. Good.
- R a1 to R a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R a2 and R a10 may be bonded to each other. Good.
- R a1 to R a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
- R a1 to R a18 are organic groups
- the organic group is not particularly limited as long as it does not impair the object of the present invention.
- a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom together with a carbon atom and a hydrogen atom.
- the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
- the organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, a carbon atom and a hydrogen atom. And a group consisting of an oxygen atom and a halogen atom.
- the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton.
- the number of carbon atoms in the organic group is preferably 1-20, more preferably 1-10, and particularly preferably 1-5.
- hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group.
- halogenated hydrocarbon group examples include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-brobro
- Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain groups such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group.
- Aralkyloxy group methoxymethyl group, ethoxymethyl group, n-propoxymethyl Group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group Alkoxymethoxy groups such as 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4 Alkoxyalkoxy such as -methoxy-n-butyloxy group, 4-
- R a1 to R a18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. It is more preferable that R a1 to R a18 are all hydrogen atoms from the viewpoint that the cured product obtained using the adhesive composition has excellent mechanical properties.
- R a1 ⁇ R a12 are the same as R a1 ⁇ R a12 in equation (A1).
- examples of the divalent group formed when R a2 and R a10 are bonded to each other include —CH 2 — and —C (CH 3 ) 2 —. It is done.
- examples of the divalent group formed when R a2 and R a8 are bonded to each other include —CH 2 — and —C (CH 3 ) 2 —.
- alicyclic epoxy compounds represented by the formula (A1) specific examples include the following compounds 1 and 2.
- alicyclic epoxy compounds represented by the formula (A2) specific examples include bicyclononadiene diepoxide and dicyclononadiene diepoxide.
- alicyclic epoxy compounds represented by the formula (A3) specific examples of suitable compounds include S spiro [3-oxatricyclo [3.2.1.0 2,4 ] octane-6,2 '-Oxirane] and the like.
- alicyclic epoxy compounds represented by formula (A4) specific examples of suitable compounds include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4- (3-methyloxirane).
- alicyclic epoxy compounds represented by the formula (A5) specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane.
- examples of non-polymers having an epoxy group that can be used as the (A) epoxy compound include glycidyl (meth) acrylate, 2-methylglycidyl ( Epoxyalkyl (meth) acrylates such as meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n Epoxyalkyloxy such as -propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate Alkyl (meth) acrylate
- Bifunctional epoxy resin such as bis
- Type epoxy resin such as tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl, and 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct.
- the 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel Corporation).
- the polymer having an epoxy group may be a polymer obtained by polymerizing a monomer mixture having a monomer having an epoxy group or a monomer having an epoxy group, and may be a hydroxyl group, a carboxyl group, an amino group.
- an epoxy group may be introduced into a polymer having a functional group having reactivity such as an epoxy group such as epichlorohydrin.
- a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain such as 1,2-polybutadiene can also be suitably used as the polymer having an epoxy group.
- Such a partial oxide includes an epoxy group generated by oxidation of an unsaturated bond contained in the side chain.
- the polymer having an epoxy group includes a monomer having an epoxy group or a monomer having an epoxy group A polymer obtained by polymerizing a body mixture and a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain are preferred.
- Polymer of a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group Among polymers having an epoxy group, it is easy to prepare, or is a homopolymer of an (meth) acrylic acid ester having an epoxy group, from the viewpoint of applicability to a substrate of a curable composition, A copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is preferred.
- the (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Moreover, the (meth) acrylic acid ester which has an epoxy group may contain the aromatic group.
- an aliphatic (meth) acrylic acid ester having an epoxy group an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group, from the viewpoint of transparency of a cured product formed using the curable composition, an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is preferable, and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is more preferable.
- Examples of (meth) acrylic acid esters containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.
- Examples of aliphatic (meth) acrylic acid esters having a chain aliphatic epoxy group include ester groups (—O—CO—) such as epoxy alkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate. And (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in ().
- Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain.
- the number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.
- aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group examples include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meta And epoxyalkyloxyalkyl (meth) acrylates such as 5-glycidyloxy-n-hexyl (meth) acrylate and 6-glycidyloxy-n-hexyl (meth) acrylate.
- aliphatic (meth) acrylic acid ester having an alicyclic epoxy group examples include compounds represented by the following formulas (a2-1) to (a2-15). Among these, compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and compounds represented by the following formulas (a2-1) to (a2-3) are more preferable.
- R a20 represents a hydrogen atom or a methyl group
- R a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms
- R a22 represents a divalent hydrocarbon having 1 to 10 carbon atoms.
- t represents an integer of 0 to 10.
- R a21 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group.
- R a22 for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a cyclohexylene group are preferable.
- any of a homopolymer of (meth) acrylic acid ester having an epoxy group and a copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is used.
- the content of the unit derived from the (meth) acrylic acid ester having an epoxy group in the polymer having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % Or more is particularly preferable, and 100% by mass is most preferable.
- the polymer having an epoxy group is a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer
- the other monomer has an unsaturated carboxylic acid or an epoxy group.
- examples thereof include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more.
- the copolymer preferably contains no unit derived from an unsaturated carboxylic acid.
- unsaturated carboxylic acid examples include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.
- Examples of (meth) acrylic acid esters having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like.
- (meth) acrylic acid esters not having an epoxy group (meth) acrylic acid esters having a group having an alicyclic skeleton are in view of the transparency of a cured product formed using a curable composition. preferable.
- the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic.
- the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group.
- the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
- Examples of the (meth) acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a3-1) to (a3-8). Among these, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and compounds represented by the following formula (a3-3) or (a3-4) are more preferable.
- R a23 represents a hydrogen atom or a methyl group
- R a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms
- R a25 represents a hydrogen atom or 1 carbon atom.
- R a24 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group.
- R a25 is preferably a methyl group or an ethyl group.
- Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.
- allyl compounds include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Etc.
- vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxy Alkyl vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4- Dichloro And the like; phenyl ether, vinyl naphthyl ether, vinyl aryl
- vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Examples thereof include phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl- ⁇ -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
- styrenes examples include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene.
- Alkyl styrene such as ethoxymethyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Methyl styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.
- the polymer having an unsaturated aliphatic hydrocarbon in the side chain is not particularly limited, but 1,2-polybutadiene having a vinyl group in the side chain is preferred because it is easily available and synthesized.
- 1,2-polybutadiene having a vinyl group in the side chain is preferred because it is easily available and synthesized.
- an epoxidized polybutadiene having an oxiranyl group and a vinyl group in the side chain is obtained.
- the ratio of oxiranyl groups in such epoxidized polybutadiene is preferably 10 to 70 mol%, more preferably 10 to 50 mol%, more preferably 10 to 40 mol%, based on the total number of moles of oxiranyl groups and vinyl groups. preferable.
- As the epoxidized polybutadiene JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be preferably used.
- the molecular weight of the polymer having an epoxy group described above is not particularly limited as long as it does not impair the object of the present invention, but the weight average molecular weight in terms of polystyrene is preferably 3,000 to 30,000, preferably 5,000 to 15,000 is more preferable.
- the content of the (A) epoxy compound in the curable composition is preferably 40 to 80% by mass, preferably 45 to 70% by mass, based on the total mass of components other than the (S) solvent in the curable composition. Is more preferable.
- the curable composition essentially contains an imidazole compound represented by the following formula (1) as a component for curing the epoxy compound (A).
- an imidazole compound represented by the following formula (1) as a component for curing the epoxy compound (A).
- the curable composition gives a cured product having excellent mechanical properties even when cured at a low temperature of about 100 to 160 ° C. for a short time.
- R 1 is a hydrogen atom or an alkyl group
- R 2 is an aromatic group that may have a substituent
- R 3 is an alkylene group that may have a substituent.
- R 4 is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is 0 to It is an integer of 3.
- R 1 is a hydrogen atom or an alkyl group.
- the alkyl group may be a linear alkyl group or a branched alkyl group.
- the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5.
- alkyl group suitable as R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, Isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-n-n-
- R 2 is an aromatic group that may have a substituent.
- the aromatic group that may have a substituent may be an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent.
- the kind of the aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
- the aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, and may be two or more aromatic hydrocarbon groups. May be formed by a single bond.
- a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.
- the type of the aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired.
- the aromatic heterocyclic group may be a monocyclic group or a polycyclic group.
- a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.
- Examples of the substituent that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, and organic group.
- the plurality of substituents may be the same or different.
- the organic group examples include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group.
- This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group.
- the organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.
- the two substituents bonded on the adjacent carbon atom may be bonded to form a cyclic structure.
- the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.
- the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes an oxygen atom, a nitrogen atom, a silicon atom, and the like.
- a bond containing a hetero atom may be included.
- the bond containing a hetero atom which the organic group may have, from the viewpoint of heat resistance of the imidazole compound represented by the formula (1), an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide Bond, amino bond (—NR—: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (—N ⁇ C (—R) —, —C ( ⁇ NR) —: R represents a hydrogen atom Or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.
- the type of substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
- substituents other than hydrocarbon groups include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups.
- Alkoxycarbonyl group amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether group and the like.
- the hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.
- Examples of the substituent of the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group include alkyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Are preferably an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.
- the imidazole compound represented by the formula (1) can be synthesized inexpensively and easily, and the solubility of the imidazole compound in water or an organic solvent is good.
- Group, furyl group and thienyl group are preferred.
- R 3 is an alkylene group which may have a substituent.
- the substituent which the alkylene group may have is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, and a halogen atom.
- the alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred.
- the number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent that is bonded to the alkylene group.
- the alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group.
- the number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.
- the amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group.
- the alkyl group contained in the monoalkylamino group or dialkylamino group may be a linear alkyl group or a branched alkyl group.
- the number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.
- alkylene group suitable as R 3 include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, n-butane.
- R 4 is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is 0 to 3 Is an integer. When n is an integer of 2 to 3, the plurality of R 4 may be the same or different.
- R 4 is an organic group
- the organic group is the same as the organic group that the aromatic group may have as a substituent for R 2 .
- R 4 is an organic group
- the organic group is preferably an alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
- alkyl group a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable.
- aromatic hydrocarbon group a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
- a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.
- a furyl group and a thienyl group are more preferable.
- R 4 is an alkyl group
- the bonding position of the alkyl group on the imidazole ring is preferably any of the 2-position, 4-position, and 5-position, and more preferably the 2-position.
- R 4 is an aromatic hydrocarbon group or an aromatic heterocyclic group
- the bonding position of these groups on imidazole is preferably the 2-position.
- the compounds represented by the following formula (1-1) are preferable because they can be synthesized inexpensively and easily and have excellent solubility in water and organic solvents.
- a compound represented by the formula (1-1), wherein R 3 is a methylene group is more preferable.
- R 1 , R 3 , R 4 , and n are the same as in Formula (1), and R 5 , R 6 , R 7 , R 8 , and R 9 are each independently Hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group A group, an ammonio group, or an organic group, provided that at least one of R 5 , R 6 , R 7 , R 8 , and R 9 is a group other than a hydrogen atom.
- R 5 , R 6 , R 7 , R 8 , and R 9 are organic groups
- the organic group is the same as the organic group that R 2 in Formula (1) has as a substituent.
- R 5 , R 6 , R 7 and R 8 are preferably a hydrogen atom from the viewpoint of solubility of the imidazole compound in a solvent.
- R 5 , R 6 , R 7 , R 8 , and R 9 are preferably the following substituent, and R 9 is particularly preferably the following substituent.
- R 9 is the following substituent
- R 5 , R 6 , R 7 and R 8 are preferably hydrogen atoms.
- —O—R 10 R 10 is a hydrogen atom or an organic group.
- R 10 is an organic group
- the organic group is the same as the organic group that R 2 in Formula (1) has as a substituent.
- R 10 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
- R 1 , R 4 , and n are the same as in Formula (1), and R 11 , R 12 , R 13 , R 14 , and R 15 are each independently , Hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group Or an organic group, provided that at least one of R 11 , R 12 , R 13 , R 14 , and R 15 is a group other than a hydrogen atom.
- R 11 , R 12 , R 13 , R 14 , and R 15 is a group represented by the aforementioned —O—R 10. It is preferable that R 15 is a group represented by —O—R 10 .
- R 15 is a group represented by —O—R 10
- R 11 , R 12 , R 13 , and R 14 are preferably hydrogen atoms.
- the method for synthesizing the imidazole compound represented by the above formula (1) is not particularly limited.
- the halogen-containing carboxylic acid derivative represented by the following formula (I) and the imidazole compound represented by the following formula (II) are reacted according to a conventional method to perform imidazolylation, whereby the above formula (1)
- the imidazole compound represented by can be synthesized.
- R 1 , R 2 , R 3 , R 4 and n are the same as in formula (1).
- Hal is a halogen atom.
- the imidazole compound is a compound represented by the formula (1) and R 3 is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (1-2),
- the imidazole compound can also be synthesized by the method using the Michael addition reaction described.
- a Michael addition reaction is caused by mixing a 3-substituted acrylic acid derivative represented by the following formula (III) and an imidazole compound represented by the above formula (II) in a solvent. Gives an imidazole compound represented by the above formula (1-2).
- an imidazole compound represented by the following formula (1-3) can be obtained by adding a 3-substituted acrylic acid derivative containing an imidazolyl group represented by the following formula (IV) to a solvent containing water. .
- R 2 is the same as in formula (1).
- imidazole compound represented by the formula (1) include the following.
- Content of (B) imidazole compound in a curable composition is not specifically limited in the range which does not inhibit the objective of this invention.
- the content of the (B) imidazole compound in the curable composition is preferably 0.1 to 20% by mass relative to the total mass of components other than the (S) solvent in the curable composition, 0.2 Is more preferably from 15 to 15% by weight, particularly preferably from 0.5 to 10% by weight, and most preferably from 1 to 7% by weight.
- the curable composition may contain (C) a crosslinking agent.
- the crosslinking agent is at least one selected from the group consisting of a polyvalent amine compound and a polyvalent carboxylic anhydride.
- a crosslinking agent participates in hardening of a curable composition by reacting with the epoxy group which (A) epoxy compound has, and (A) an epoxy compound is bridge
- a curable composition can be hardened more favorably at low temperature.
- the polyvalent amine compound and the polyvalent carboxylic acid anhydride can be appropriately selected from polyvalent amine compounds and polyvalent carboxylic acid anhydrides conventionally used as curing agents for epoxy compounds.
- the polyvalent amine compound and the polyvalent carboxylic acid anhydride will be described.
- the polyvalent amine compound is not particularly limited as long as it can form a cured product by reacting with the (A) epoxy compound.
- the polyvalent amine compound may be a compound that can react with the epoxy compound (A) as it is, or a so-called latent curing agent that can react with the epoxy compound (A) when activated by heating. Also good.
- Preferable examples of the polyvalent amine compound include aromatic diamine, guanidine, substituted guanidine, biguanidine, substituted biguanidine, substituted urea, melamine resin, and guanamine derivatives.
- aromatic diamine examples include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethermethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5- Diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenyld
- Substituted guanidine is a compound in which a hydrogen atom bonded to a nitrogen atom contained in guanidine is substituted with an organic group.
- the organic group may contain heteroatoms such as N, O, S, P, and halogen atoms.
- a hydrocarbon group or a cyano group is preferable.
- the hydrocarbon group an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
- Suitable substituted guanidines include methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, and dicyandiamide. Of these, dicyandiamide is preferred.
- Substituted biguanidine is a compound in which a hydrogen atom bonded to a nitrogen atom contained in biguanidine is substituted with an organic group.
- the organic group may contain heteroatoms such as N, O, S, P, and halogen atoms.
- the organic group bonded to the nitrogen atom of the substituted biguanidine is preferably a hydrocarbon group or a cyano group.
- the hydrocarbon group an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
- Suitable substituted biguanidines include methyl biguanidine, dimethyl biguanidine, tetramethyl biguanidine, hexamethyl biguanidine, and heptamethyl biguanidine.
- Substituted urea is a compound in which a hydrogen atom bonded to a nitrogen atom contained in urea is substituted with an organic group.
- the organic group may contain heteroatoms such as N, O, S, P, and halogen atoms.
- the substituted urea may be a urea dimer represented by the following formula (C1).
- X 1 to X 6 are each independently a hydrogen atom or an organic group, and X 7 is a divalent organic group.
- substituted urea examples include N, N-dimethyl-N ′-(3-chloro-4-methylphenyl) urea, N, N-dimethyl-N ′-(4-chlorophenyl) urea, N, N -Dimethyl-N '-(3,4-dichlorophenyl) urea, N, N-dimethyl-N'-phenylurea, 2,4-bis (N', N'-dimethylureido) toluene, 1,4-bis ( N ', N'-dimethylureido) benzene, dimethylpropyleneurea, and 1,3-hydroxymethylurea.
- guanamine derivatives include alkylated benzoguanamine resins, benzoguanamine resins, and methoxymethylethoxymethylbenzoguanamine resins.
- polyvalent amine compounds used as the crosslinking agent (C) described above at least one selected from the group consisting of guanidine, substituted guanidine, and aromatic diamine is preferable.
- the polyvalent carboxylic acid anhydride can be appropriately selected from various acid anhydride compounds conventionally used as curing agents for epoxy resins.
- Specific examples of the polyvalent carboxylic acid anhydride include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic acid Examples thereof include anhydride, trimellitic anhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and styrene-maleic anhydride copolymer.
- the polyvalent carboxylic acid anhydride is preferably a compound that is liquid at room temperature.
- the content of the (C) crosslinking agent in the curable composition is preferably 20% by mass or less, and preferably 0.1 to 20% by mass with respect to the total mass of components other than the (S) solvent in the curable composition. % Is more preferable, and 0.1 to 10% by mass is particularly preferable.
- the curable composition may contain (D) a curing accelerator.
- a curing accelerator include oxime ester compounds, ⁇ -aminoalkylphenone compounds, acyl phosphine oxide compounds, and imidazole compounds.
- the oxime ester compound is not particularly limited as long as it is a compound in which two organic groups are bonded through an oxime ester bond represented by ⁇ N—O—CO—.
- Suitable oxime ester compounds include the following compounds:
- ⁇ -aminoalkylphenone compounds include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
- imidazole compound examples include 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (2MA- OK, manufactured by Shikoku Chemicals Co., Ltd.), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (2MZ-A, manufactured by Shikoku Chemicals Co., Ltd.), 2 -Phenyl-4,5-dihydroxymethylimidazole (2PHZ, manufactured by Shikoku Kasei Co., Ltd.) 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
- the oxime ester compound, ⁇ -aminoalkylphenone compound, and acylphosphine oxide compound may be used together with an auxiliary agent that further enhances the curing acceleration effect.
- adjuvants include benzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 4,4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, Benzophenones such as 3,4-dimethylbenzophenone, 4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3,3-dimethyl-4-methoxybenzophenone, and 4-phenylbenzophenone; acetophenone, 4-methoxyacetophenone, 2,4 -Dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxya Acetophenones such as tophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, and 4-phenylacetophen
- the content of the (D) curing accelerator in the curable composition is preferably 0.1 to 10% by mass relative to the total mass of components other than the (S) solvent in the curable composition. 1 to 5% by mass is more preferable.
- content of the adjuvant in a curable composition is with respect to the sum total of the mass of components other than the (S) solvent in a curable composition. Therefore, 0.1 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.
- the curable composition may contain additives such as a filler such as rubber particles, a surfactant, a thermal polymerization inhibitor, an antifoaming agent, and a silane coupling agent, if necessary. Any additive can be used as the additive.
- the surfactant include anionic, cationic, and nonionic compounds
- examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether
- examples of the antifoaming agent include silicone and fluorine. Compounds and the like.
- the curable composition may contain a (S) solvent for improving the coating property and adjusting the viscosity.
- the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether,
- the content of the (S) solvent in the curable composition is not particularly limited.
- the content of the (S) solvent in the curable composition is appropriately adjusted in consideration of the handleability of the curable composition such as applicability.
- the concentration of components other than the (S) solvent in the curable composition is typically preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more.
- a curable composition can be produced by uniformly mixing the components described above at a predetermined ratio. Moreover, when a curable composition contains the above-mentioned (B) component and (C) component, after preparing the hardening
- the curing agent mixture composition may contain a solvent for the purpose of adjusting the viscosity. As a solvent, the solvent which can be used as said (S) component can be used. Details of the hardener mixture composition will be described later.
- Examples of the mixing device that can be used for producing the curable composition include a two-roll and a three-roll. Since the curable composition containing each component described above cures at a low temperature of about 130 ° C. in a short time, the mixing operation when preparing the curable composition is performed at room temperature to about 40 ° C. preferable. When the viscosity of the curable composition is sufficiently low, if necessary, the curable composition may be filtered using a filter having an opening of a desired size in order to remove insoluble foreign substances.
- the curable composition produced in this way can be cured at a low temperature in a short time and has a long pot life. Moreover, since this curable composition adhere
- the temperature and time for curing the curable composition described above are not particularly limited as long as the curing proceeds sufficiently, but the above curable composition can be cured at a low temperature in a short time. Specifically, the curable composition is cured at a temperature of about 100 to 160 ° C. and a time of about 3 to 10 minutes. In addition, although said curable composition can be hardened at low temperature, it can also be hardened at high temperature.
- the curing temperature of the curable composition is not particularly limited as long as it does not cause thermal decomposition of components contained in the curable composition or volatilization or sublimation of components other than the (S) solvent.
- the curable composition demonstrated above contains the (A) epoxy compound conventionally mix
- the method of using the adhesive is the same as that of an adhesive containing a conventional epoxy compound.
- As a specific bonding method after applying or injecting an adhesive to at least one predetermined position of a plurality of adherends, the plurality of adherends are fixed in a desired state, and then the plurality of adherends are heated. The method of doing is mentioned.
- the cured product of the curable composition adheres well to various materials.
- the curable composition demonstrated above can also be used as a sealing material of electronic components like various semiconductor elements, for example.
- the curable composition demonstrated above can be used suitably as a material for forming a matrix in the fiber reinforced composite material which consists of a matrix and a reinforced fiber.
- the reinforcing fiber is not particularly limited as long as it has been conventionally used for the production of fiber-reinforced composite materials.
- the reinforcing fiber may be a twisted yarn, an untwisted yarn, or a non-twisted yarn, and an untwisted yarn or a non-twisted yarn is preferred from the moldability and mechanical strength of the fiber-reinforced composite material.
- the form of the reinforcing fibers is not particularly limited, and the short fibers of the reinforcing fibers may be dispersed in the matrix.
- the weaving method can be freely selected from plain weaving, satin weaving, and the like according to the part to be used and the application.
- the reinforcing fiber examples include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like because of the mechanical strength and durability of the fiber-reinforced composite material.
- Reinforcing fibers may be used in combination of two or more.
- carbon fibers are preferable because the strength of the fiber-reinforced composite material is particularly excellent.
- As the carbon fiber polyacrylonitrile, pitch, rayon, or the like can be used. Among these carbon fibers, polyacrylonitrile-based carbon fibers are preferable.
- the volume content of the reinforcing fiber in the fiber-reinforced composite material comprising the matrix and the reinforcing fiber is appropriately selected according to the strength and shape of the fiber-reinforced composite material, but is typically 40 to 85% by volume. Of these, 50 to 70% by volume is more preferable.
- the method for producing the fiber reinforced composite material is not particularly limited. According to a well-known method, a fiber reinforced composite material is produced by impregnating a curable composition into reinforcing fibers and then curing the curable composition under predetermined conditions. Since the above curable composition is cured at a low temperature in a short time, by using the above curable composition, it is possible to produce a fiber reinforced composite material at a high cycle while reducing energy required for curing. Is possible.
- the curing agent mixed composition is selected from the group consisting of (B) an imidazole compound (component (B)) represented by the following formula (1), (C) a polyvalent amine compound and a polyvalent carboxylic acid anhydride. And at least one crosslinking agent (component (C)).
- R 1 is a hydrogen atom or an alkyl group
- R 2 is an aromatic group that may have a substituent
- R 3 is an alkylene group that may have a substituent.
- R 4 is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is 0 to It is an integer of 3.
- the imidazole compound represented by the following formula (1) and (C) at least one cross-linking agent selected from the group consisting of a polyvalent amine compound and a polyvalent carboxylic acid anhydride are all curable. It is as having mentioned above as a component of a composition.
- the mass ratio of the component (B) and the component (C) in the hardener mixture composition is not particularly limited, but the mass of the component (B): the mass of the component (C) is 0.1: 99. 9 to 99.9: 0.1 is preferable, and 0.5: 99.5 to 99.5: 0.5 is more preferable.
- the curing agent mixed composition may contain the above-mentioned (D) curing accelerator ((D) component) and (E) other components ((E) component) as necessary.
- the contents of (D) curing accelerator and (E) other components in the curing agent mixture composition are appropriately determined in consideration of the composition of the curable composition prepared using the curing agent mixture composition. It is done.
- the curing agent mixture composition may contain the aforementioned (S) solvent.
- the curing agent mixture composition may be a solution or a slurry (paste).
- the curing agent mixture composition is preferably a solution.
- the content of the (S) solvent in the curing agent mixture composition is not particularly limited.
- the content of the (S) solvent in the curing agent mixture composition is preferably 0.1 to 99% by mass, more preferably 1 to 95% by mass, and particularly preferably 10 to 80% by mass. preferable.
- the method for preparing the curing agent mixed composition is not particularly limited.
- the hardener mixture composition does not contain the (S) solvent
- the powder of the component (B), the powder of the component (C), and optionally the powder of the component (D), and / or Or the powder of (E) component is mixed and a hardening
- a powder mixing apparatus that can be used for the preparation of the hardener mixture composition, a well-known powder mixing apparatus such as a planetary mixer, a ribbon blender, a radige mixer, a Henschel mixer, a rocking mixer, and a Nauta mixer (registered trademark) may be used. it can.
- the melts or the melt and powder may be mixed.
- the components of the curing agent mixture composition are mixed at a temperature lower than the lowest thermal decomposition temperature among the thermal decomposition temperatures of the components contained in the curing agent mixture composition.
- the hardener mixture composition contains the (S) solvent
- the hardener mixture composition is obtained by uniformly mixing these components after adding a component other than the (S) solvent to the (S) solvent. Can be prepared.
- the components of the curing agent mixture composition may be heated to a temperature that does not thermally decompose, or may have a low solid content concentration (for example, 1 to 30). The composition may be concentrated by evaporating the solvent or the like after preparing the curing agent mixed composition at (mass%).
- EP1 to EP6 which are (A) epoxy compounds
- the number on the lower right of the parentheses in each repeating unit represents the content (% by mass) of each unit in the epoxy group-containing resin that is EP-6, and the mass average molecular weight is 7,000.
- CA1 to CA4 were used as (C) crosslinking agents.
- CA1 dicyandiamide
- CA2 4,4′-diaminodiphenyl ether
- CA3 tetrahydrophthalic anhydride
- CA4 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- Example 10 Example 10, Example 11, and Comparative Examples 1 to 4, the types and amounts described in Table 1 were combined with three components (A), (B), and (C). Using this roll, the mixture was uniformly mixed to obtain a curable composition.
- the (A) component, (C) component, and (C) component of the types and amounts shown in Table 1 were mixed in propylene glycol monomethyl ether acetate with a solid content. It dissolved so that a density
- ⁇ Low temperature curability evaluation> The curable composition was injected into a gap having a width of 2 mm formed between the two molds. The curable composition injected into the gap was heated for 5 minutes, and then the mold was peeled off to obtain a plate-shaped test piece having a thickness of 2 mm. It was confirmed that the surface of the test piece was in a tack-free state without stickiness as a measure of curing. Those cured at a heating temperature of less than 140 ° C. are judged as ⁇ , those cured at a heating temperature of 140 ° C. or more and less than 160 ° C. are judged as ⁇ , and those that required a heating temperature of over 160 ° C. are judged as ⁇ . did.
- the curable composition containing the component (A) which is an epoxy compound and the component (B) which is an imidazole compound represented by the formula (1) can be cured at a low temperature and in a short time. There is a long pot life.
- the curable composition containing the component (A) which is an epoxy compound and the component (B) which is an imidazole compound having a structure not included in the formula (1) is obtained at a low temperature in a short time. It turns out that a good effect and a long pot life cannot be compatible.
- the curable composition further contains (C) a crosslinking agent, at least one of curability at low temperature and pot life is particularly excellent.
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Abstract
Description
また、本発明は、低温且つ短時間で硬化可能であって、ポットライフの長い硬化性組成物を与える、硬化剤混合組成物を提供することを目的とする。
また、本発明によれば、低温且つ短時間で硬化可能であって、ポットライフの長い硬化性組成物を与える、硬化剤混合組成物を提供することができる。
硬化性化合物は(A)エポキシ化合物と、(B)下記式(1)で表されるイミダゾール化合物(以下、(B)イミダゾール化合物とも記す。)とを含む。かかる硬化性組成物では、(A)エポキシ化合物と、(B)イミダゾール化合物とを組み合わせることによって、例えば、100~160℃程度の低温においても、(A)エポキシ化合物の硬化反応が著しく促進される。このため、かかる硬化性組成物は、低温での短時間の硬化であっても、機械的特性に優れる硬化物を与える。
(A)エポキシ化合物は、エポキシ基を有する化合物であれば特に限定されない。(A)エポキシ化合物は、従来から硬化性組成物に配合されているエポキシ基を有する種々の化合物から選択できる。(A)エポキシ化合物は、非重合体であるエポキシ基を有する低分子化合物であってもよく、エポキシ基を有する重合体であってもよい。以下、(A)エポキシ化合物に関して、エポキシ基を有する非重合体と、エポキシ基を有する重合体とについて順に説明する。
エポキシ基を有する非重合体としては、硬化性組成物を用いて形成される硬化物が機械的特性に優れる点から、芳香族基を含まない脂肪族エポキシ化合物が好ましい。脂肪族エポキシ化合物の中では、透明性及び硬度に優れる硬化物を与えることから、脂環式エポキシ基を有する脂肪族エポキシ化合物が好ましい。
式(A3)で表される脂環式エポキシ化合物のうち、好適な化合物の具体例としては、Sスピロ[3-オキサトリシクロ[3.2.1.02,4]オクタン-6,2’-オキシラン]等が挙げられる。
式(A4)で表される脂環式エポキシ化合物のうち、好適な化合物の具体例としては、4-ビニルシクロヘキセンジオキシド、ジペンテンジオキシド、リモネンジオキシド、1-メチルー4-(3-メチルオキシラン-2-イル)-7-オキサビシクロ[4.1.0]ヘプタン等が挙げられる。
式(A5)で表される脂環式エポキシ化合物のうち、好適な化合物の具体例としては、1,2,5,6-ジエポキシシクロオクタン等が挙げられる。
エポキシ基を有する重合体は、エポキシ基を有する単量体又はエポキシ基を有する単量体を含む単量体混合物を重合させて得られる重合体であってもよく、水酸基、カルボキシル基、アミノ基等の反応性を有する官能基を有する重合体に対して、例えばエピクロルヒドリンのようなエポキシ基を有する化合物を用いてエポキシ基を導入したものであってもよい。また、1,2-ポリブタジエンのような側鎖に不飽和脂肪族炭化水素基を有する重合体の部分酸化物もエポキシ基を有する重合体として好適に使用することができる。かかる部分酸化物は、側鎖に含まれる不飽和結合の酸化により生成したエポキシ基を含む。
エポキシ基を有する重合体の中では、調製が容易であることや、硬化性組成物の基材への塗布性等の点から、エポキシ基を有する(メタ)アクリル酸エステルの単独重合体か、エポキシ基を有する(メタ)アクリル酸エステルと他の単量体との共重合体が好ましい。
側鎖に不飽和脂肪族炭化水素を有する重合体は特に限定されないが、入手や合成が容易であること等から、側鎖にビニル基を有する1,2-ポリブタジエンが好ましい。1,2-ポリブタジエンを部分的に酸化することによって、側鎖にオキシラニル基とビニル基とを有する、エポキシ化ポリブタジエンが得られる。このようなエポキシ化ポリブタジエンにおけるオキシラニル基の比率は、オキシラニル基とビニル基との総モル数に対して10~70モル%が好ましく、10~50モル%がより好ましく、10~40モル%がより好ましい。エポキシ化ポリブタジエンとしては、日本曹達株式会社より市販される、JP-100、及びJP-200を好適に使用することができる。
硬化性組成物は、(A)エポキシ化合物を硬化させる成分として、下記式(1)で表されるイミダゾール化合物を必須に含有する。硬化性組成物は、(B)イミダゾール化合物を含有することによって、100~160℃程度の低温での短時間の硬化であっても、機械的特性に優れる硬化物を与える。
-O-R10(R10は水素原子又は有機基である。)
硬化性組成物は(C)架橋剤を含んでいてもよい。(C)架橋剤は、多価アミン化合物及び多価カルボン酸無水物からなる群より選択される少なくとも1種である。(C)架橋剤は、(A)エポキシ化合物が有するエポキシ基と反応して(A)エポキシ化合物を分子間架橋させることによって硬化性組成物を硬化に関与する。(C)架橋剤を硬化性組成物に配合することにより、硬化性組成物を低温でより良好に硬化させることができる。多価アミン化合物及び多価カルボン酸無水物は、従来からエポキシ化合物の硬化剤として使用されている多価アミン化合物及び多価カルボン酸無水物より適宜選択して使用することができる。以下、多価アミン化合物及び多価カルボン酸無水物について説明する。
多価アミン化合物は、(A)エポキシ化合物と反応して硬化物を形成可能なものであれば、特に限定されない。多価アミン化合物は、そのまま(A)エポキシ化合物と反応し得る化合物であってもよく、加熱により活性化された状態で(A)エポキシ化合物と反応し得る、所謂、潜在性硬化剤であってもよい。多価アミン化合物の好適な例としては、芳香族ジアミン、グアニジン、置換グアニジン、ビグアニジン、置換ビグアニジン、置換尿素、メラミン樹脂、及びグアナミン誘導体が挙げられる。
X1X2N-CO-NX3-X7-NX6-CO-NX4X5・・・(C1)
(式(C1)中、X1~X6は、それぞれ独立に、水素原子又は有機基であり、X7は2価の有機基である。)
多価カルボン酸無水物は、従来からエポキシ樹脂用の硬化剤として使用されている種々の酸無水物化合物から適宜選択して用いることができる。多価カルボン酸無水物の具体例としては、マレイン酸無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、4-メチルヘキサヒドロフタル酸無水物、ヘキサヒドロトリメリット酸無水物、フタル酸無水物、トリメリット酸無水物、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、スチレン-無水マレイン酸共重合体が挙げられる。別途溶剤を用いない場合には多価カルボン酸無水物は室温で液体の化合物であることが好ましい。
硬化性組成物は、(D)硬化促進剤を含んでいてもよい。硬化促進剤の好適な例としては、オキシムエステル化合物、α-アミノアルキルフェノン系化合物、アシルフォスフィンオキサイド系化合物、及びイミダゾール化合物が挙げられる。
硬化性組成物には、必要に応じて、ゴム粒子等の充填材、界面活性剤、熱重合禁止剤、消泡剤、シランカップリング剤等の添加剤を含有させることができる。いずれの添加剤も、従来公知のものを用いることができる。界面活性剤としては、アニオン系、カチオン系、ノニオン系等の化合物が挙げられ、熱重合禁止剤としては、ヒドロキノン、ヒドロキノンモノエチルエーテル等が挙げられ、消泡剤としては、シリコーン系、フッ素系化合物等が挙げられる。
硬化性組成物は、塗布性の改善や、粘度調整のため、(S)溶剤を含んでいてもよい。
以上説明した各成分を所定の比率で均一に混合することにより、硬化性組成物を製造することができる。また、硬化性組成物が、前述の(B)成分と(C)成分とを含有する場合、(B)成分と(C)成分とを含有する硬化剤混合組成物を調製した後、硬化剤混合組成物と、他の成分とを均一に混合することで硬化性組成物を製造してもよい。硬化剤混合組成物は、粘度調整の目的等で溶剤を含んでいてもよい。溶剤としては、上記(S)成分として使用できる溶剤を用いることができる。硬化剤混合組成物の詳細については後述する。
硬化性組成物の製造に用いることができる混合装置としては、二本ロールや三本ロール等が挙げられる。以上説明した各成分を含有する硬化性組成物は、130℃程度の低温で短時間で硬化するため、硬化性組成物を調製する際の混合操作は、室温~40℃程度で行われるのが好ましい。硬化性組成物の粘度が十分に低い場合、必要に応じて、不溶性の異物を除去するために、所望のサイズの開口を有するフィルターを用いて硬化性組成物をろ過してもよい。
以上説明した硬化性組成物を硬化させる際の温度及び時間は、硬化が十分に進行する限り特に限定されないが、上記の硬化性組成物は低温短時間で硬化可能である。具体的には、100~160℃程度の温度、3分~10分程度の時間で、硬化性組成物が硬化される。なお、上記の硬化性組成物は低温で硬化可能であるが、高温で硬化させることもできる。硬化性組成物の硬化温度は、硬化性組成物に含まれる成分の熱分解や、(S)溶剤以外の成分の揮発や昇華が生じない温度であれば特に限定されない。
以上説明した硬化性組成物は、従来から種々の接着剤に配合されている(A)エポキシ化合物を含有するため、種々の材料を接着するための接着剤として良好に使用可能である。接着剤の使用方法は、従来のエポキシ化合物を含有する接着剤と同様である。具体的な接着方法としては、複数の被着物における少なくとも一方の所定の箇所に、接着剤を塗布又は注入した後、複数の被着物を所望する状態に固定し、次いで、複数の被着物を加熱する方法が挙げられる。
以上説明した硬化性組成物は、マトリックスと、強化繊維とからなる繊維強化複合材料における、マトリックスを形成するための材料として好適に使用することができる。
硬化剤混合組成物は、(B)下記式(1)で表されるイミダゾール化合物((B)成分)と、(C)多価アミン化合物及び多価カルボン酸無水物からなる群より選択される少なくとも1種の架橋剤((C)成分)と、を含有する。かかる硬化剤組成物を、前述の(A)エポキシ化合物、又は(A)エポキシ化合物を含有する組成物に配合することにより、低温且つ短時間で硬化可能であって、ポットライフの長い硬化性組成物を得ることができる。
硬化性組成物を調製する際、2種以上の硬化剤混合組成物を組み合わせて用いてもよい。
硬化剤混合組成物中の、(B)成分と、(C)成分との質量比は、特に限定されないが、(B)成分の質量:(C)成分の質量として、0.1:99.9~99.9:0.1が好ましく、0.5:99.5~99.5:0.5がより好ましい。
硬化剤混合組成物中の(S)溶剤の含有量は特に限定されない。(S)溶剤を含む場合、硬化剤混合組成物中の(S)溶剤の含有量は、0.1~99質量%が好ましく、1~95質量%がより好ましく、10~80質量%が特に好ましい。
硬化剤混合組成物の調製に使用できる粉体混合装置としては、プラネタリーミキサ 、リボンブレンダ、レーディゲミキサ、ヘンシェルミキサ、ロッキングミキサ、及びナウタミキサ(登録商標)等の周知の粉体混合装置を用いることができる。
実施例及び比較例では、(A)成分として、(A)エポキシ化合物である下記のEP1~EP6を用いた。EP-6について、各繰り返し単位中の括弧の右下の数字は、EP-6であるエポキシ基含有樹脂中での各単位の含有量(質量%)を表し、質量平均分子量は7000である。
以下の方法に従って、上記のB1を合成した。
まず、下記式の化合物30gをメタノール200gに溶解させた後、メタノール中に水酸化カリウム7gを添加した。次いで、メタノール溶液を40℃で撹拌した。メタノールを留去し、残渣を水200gに懸濁させた。得られた懸濁液にテトラヒドロフラン200gを混合、撹拌し、水相を分液した。氷冷下、塩酸4gを添加、撹拌した後に酢酸エチル100gを混合、撹拌した。混合液を静置した後、油相を分取した。油相から目的物を晶析させ、析出物を回収して、上記構造のB1を得た。
1H-NMR(DMSO):11.724(s,1H),7.838(s,1H),7.340(d,2H,J=4.3Hz),7.321(d,1H,J=7.2Hz),6.893(d,2H,J=4.3Hz),6.876(d,1H,J=6.1Hz),5.695(dd,1H,J=4.3J,3.2J),3.720(s,3H),3.250(m,2H)
CA1:ジシアンジアミド
CA2:4,4’-ジアミノジフェニルエーテル
CA3:テトラヒドロフタル酸無水物
CA4:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
2枚の金型の間に形成された幅2mmの隙間に、硬化性組成物を注入した。隙間に注入された硬化性組成物を、5分間加熱した後、金型を剥離して、厚さ2mmの板状の試験片を得た。試験片の表面がべたつきのないタックフリーの状態となっていることを硬化の目安として確認を行った。
加熱温度が140℃未満で硬化したものを◎と判定し、加熱温度が140℃以上160℃未満で硬化したものを○と判定し、加熱温度が160℃超必要であったものを×と判定した。
硬化性組成物の調製直後の粘度(cP)を、E型粘度計(TV-20型、コーンプレートタイプ、東機産業株式会社製)を用いて測定した。また、硬化性組成物の粘度を、25℃で10日保存した後と、30日保存した後に測定した。10日保存後の粘度が初期粘度より20cP以上増加していた場合を×と判定した。10日保存後の粘度の初期粘度に対する増加は20cP未満であるが、30日保存後の粘度が初期粘度よりも20cP以上増加していた場合を○と判定した。30日保存後の粘度の初期粘度に対する増加が20cP未満である場合を◎と判定した。
Claims (7)
- (C)多価アミン化合物及び多価カルボン酸無水物からなる群より選択される少なくとも1種の架橋剤を含む、請求項1に記載の硬化性組成物。
- 前記(C)架橋剤がグアニジン、置換グアニジン、及び/又は芳香族ジアミンである請求項1に記載の硬化性組成物。
- 請求項1~3のいずれか1項に記載の硬化性組成物からなる接着剤。
- 強化繊維に含浸された請求項1~3のいずれか1項に記載の硬化性組成物を加熱により硬化させる、繊維強化複合材料の製造方法。
- 請求項1~3のいずれか1項に記載の硬化性組成物の硬化物からなるマトリックスと、強化繊維とからなる、繊維強化複合材料。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3184511A4 (en) * | 2014-08-29 | 2017-07-26 | Tokyo Ohka Kogyo Co., Ltd. | Imidazole compound, metal surface treatment liquid, metal surface treatment method, and laminate production method |
JP2017149702A (ja) * | 2016-02-26 | 2017-08-31 | 東京応化工業株式会社 | カルボン酸エステルの製造方法、エステル化剤、及び開環付加触媒 |
EP3330320A4 (en) * | 2015-08-07 | 2018-10-17 | Tokyo Ohka Kogyo Co., Ltd. | Polyimide precursor composition |
US10696845B2 (en) | 2015-03-27 | 2020-06-30 | Tokyo Ohka Kogyo Co., Ltd. | Energy-sensitive resin composition |
US11718587B2 (en) * | 2017-09-29 | 2023-08-08 | Tokyo Ohka Kogyo Co., Ltd. | Compound, epoxy curing catalyst and method for producing compound |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005516115A (ja) * | 2002-01-31 | 2005-06-02 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレーション | 非フローアンダーフィルカプセル封止材料 |
WO2013081060A1 (ja) * | 2011-11-29 | 2013-06-06 | 三菱レイヨン株式会社 | エポキシ樹脂組成物、プリプレグ、繊維強化複合材料とその製造方法 |
JP2013253233A (ja) * | 2012-05-10 | 2013-12-19 | Nippon Synthetic Chem Ind Co Ltd:The | アニオン硬化性化合物用硬化剤、硬化性組成物、硬化物、及び新規イミダゾール系化合物 |
JP2014118576A (ja) * | 2012-12-18 | 2014-06-30 | Air Products And Chemicals Inc | 溶媒和された固体を使用するエポキシ樹脂組成物 |
JP2015110560A (ja) * | 2013-11-05 | 2015-06-18 | 日本合成化学工業株式会社 | 新規イミダゾール系化合物 |
JP2015214608A (ja) * | 2014-05-07 | 2015-12-03 | 学校法人東京理科大学 | 塩基増殖剤及び当該塩基増殖剤を含有する塩基反応性樹脂組成物 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997028210A1 (fr) * | 1996-02-02 | 1997-08-07 | Toray Industries, Inc. | Compositions de resines pour materiaux composites a renfort de fibres et leurs procedes de fabrication, pre-impregnes, composites a renfort de fibres, et structures en nids d'abeilles |
BR112013009345A2 (pt) | 2010-11-08 | 2015-04-22 | Toray Industries | Composição de resina epóxi, prepreg, material compósito reforçado com fibra e método de fabricação. |
US9309381B2 (en) | 2011-06-24 | 2016-04-12 | Air Products And Chemicals, Inc. | Epoxy resin compositions using solvated solids |
RU2692774C2 (ru) * | 2014-08-29 | 2019-06-27 | Дайсел Корпорэйшн | Имидазольное соединение, жидкость для обработки металлической поверхности, способ обработки металлической поверхности и способ изготовления ламината |
JP6723698B2 (ja) * | 2015-07-23 | 2020-07-15 | 東京応化工業株式会社 | 微粒子含有組成物 |
WO2017026448A1 (ja) * | 2015-08-07 | 2017-02-16 | 東京応化工業株式会社 | ポリイミド前駆体組成物 |
-
2015
- 2015-12-08 WO PCT/JP2015/084451 patent/WO2016093254A1/ja active Application Filing
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005516115A (ja) * | 2002-01-31 | 2005-06-02 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレーション | 非フローアンダーフィルカプセル封止材料 |
WO2013081060A1 (ja) * | 2011-11-29 | 2013-06-06 | 三菱レイヨン株式会社 | エポキシ樹脂組成物、プリプレグ、繊維強化複合材料とその製造方法 |
JP2013253233A (ja) * | 2012-05-10 | 2013-12-19 | Nippon Synthetic Chem Ind Co Ltd:The | アニオン硬化性化合物用硬化剤、硬化性組成物、硬化物、及び新規イミダゾール系化合物 |
JP2014118576A (ja) * | 2012-12-18 | 2014-06-30 | Air Products And Chemicals Inc | 溶媒和された固体を使用するエポキシ樹脂組成物 |
JP2015110560A (ja) * | 2013-11-05 | 2015-06-18 | 日本合成化学工業株式会社 | 新規イミダゾール系化合物 |
JP2015214608A (ja) * | 2014-05-07 | 2015-12-03 | 学校法人東京理科大学 | 塩基増殖剤及び当該塩基増殖剤を含有する塩基反応性樹脂組成物 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3184511A4 (en) * | 2014-08-29 | 2017-07-26 | Tokyo Ohka Kogyo Co., Ltd. | Imidazole compound, metal surface treatment liquid, metal surface treatment method, and laminate production method |
US10336708B2 (en) | 2014-08-29 | 2019-07-02 | Tokyo Ohka Kogyo Co., Ltd. | Imidazole compound, metal surface treatment liquid, metal surface treatment method, and laminate production method |
US10696845B2 (en) | 2015-03-27 | 2020-06-30 | Tokyo Ohka Kogyo Co., Ltd. | Energy-sensitive resin composition |
EP3330320A4 (en) * | 2015-08-07 | 2018-10-17 | Tokyo Ohka Kogyo Co., Ltd. | Polyimide precursor composition |
US10954340B2 (en) | 2015-08-07 | 2021-03-23 | Tokyo Ohka Kogyo Co., Ltd. | Polyimide precursor composition |
JP2017149702A (ja) * | 2016-02-26 | 2017-08-31 | 東京応化工業株式会社 | カルボン酸エステルの製造方法、エステル化剤、及び開環付加触媒 |
US11718587B2 (en) * | 2017-09-29 | 2023-08-08 | Tokyo Ohka Kogyo Co., Ltd. | Compound, epoxy curing catalyst and method for producing compound |
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