JP2017066076A - 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound, synthesis method and epoxy resin curing agent - Google Patents
1,3,4,6-tetrakis (aminoalkyl) glycoluril compound, synthesis method and epoxy resin curing agent Download PDFInfo
- Publication number
- JP2017066076A JP2017066076A JP2015192481A JP2015192481A JP2017066076A JP 2017066076 A JP2017066076 A JP 2017066076A JP 2015192481 A JP2015192481 A JP 2015192481A JP 2015192481 A JP2015192481 A JP 2015192481A JP 2017066076 A JP2017066076 A JP 2017066076A
- Authority
- JP
- Japan
- Prior art keywords
- tetrakis
- glycoluril
- glycoluril compound
- compound
- aminoalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 glycoluril compound Chemical class 0.000 title claims abstract description 73
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 125000004103 aminoalkyl group Chemical group 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title description 2
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000004966 cyanoalkyl group Chemical group 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical class N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 22
- 239000004593 Epoxy Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 9
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 5
- 125000004042 4-aminobutyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])N([H])[H] 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical class [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
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- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
本発明は、１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物と、該化合物の合成方法および該化合物を成分とするエポキシ樹脂用硬化剤に関する。 The present invention relates to a 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound, a method for synthesizing the compound, and a curing agent for an epoxy resin containing the compound as a component.
グリコールウリル化合物は、その骨格（グリコールウリル環）中に４つの尿素系窒素を有し、且つ対称性の高い構造を具備する複素環化合物であるが、この尿素系窒素の反応性を利用して、種々の官能基が導入されたグリコールウリル化合物が合成されている。そして、このようなグリコールウリル化合物の多くは、樹脂の添加剤（架橋剤、改質剤）としての検討または利用が進められている。 A glycoluril compound is a heterocyclic compound having four urea nitrogens in its skeleton (glycoluril ring) and a highly symmetric structure. By utilizing the reactivity of this urea nitrogen, A glycoluril compound into which various functional groups have been introduced has been synthesized. Many of these glycoluril compounds have been studied or used as resin additives (crosslinking agents, modifiers).
例えば、特許文献１には、テトラキスメトキシメチルグリコールウリルと、ポリエステル樹脂を含有する粉末塗料組成物が提案されている。
特許文献２には、合成樹脂あるいは合成ゴム等の架橋剤、または難燃剤等の中間体としての利用が期待されるテトラアリルグリコールウリル化合物が提案されている。
特許文献３には、テトラキス（カルボキシアルキル）グリコール化合物を含有するエポキシ樹脂組成物が提案されている。
特許文献４には、グリシジルグリコールウリル化合物を含有するエポキシ樹脂組成物が提案されている。
特許文献５には、光硬化性樹脂の架橋剤としての利用が期待されるテトラキス（（メタ）アクリロイルオキシアルキル）グリコールウリルが提案されている。
特許文献６には、メルカプトアルキルグリコールウリル化合物を含有するエポキシ樹脂組成物が提案されている。
特許文献７には、分子中にグリコールウリル環を含むオルガノシランが提案され、更に、分子中にグリコールウリル環を含み、必要に応じて、分子中にヒドロシリル基を有するオルガノシロキサンが提案されている。
特許文献８には、分子中に１〜３つのアリル基を有するアリルグリコールウリル化合物が提案されている。
For example,
Patent Document 2 proposes a tetraallylglycoluril compound that is expected to be used as a crosslinking agent such as a synthetic resin or synthetic rubber, or an intermediate such as a flame retardant.
Patent Document 3 proposes an epoxy resin composition containing a tetrakis (carboxyalkyl) glycol compound.
Patent Document 4 proposes an epoxy resin composition containing a glycidyl glycoluril compound.
Patent Document 5 proposes tetrakis ((meth) acryloyloxyalkyl) glycoluril, which is expected to be used as a crosslinking agent for a photocurable resin.
Patent Document 6 proposes an epoxy resin composition containing a mercaptoalkylglycoluril compound.
Patent Document 7 proposes an organosilane containing a glycoluril ring in the molecule, and further proposes an organosiloxane containing a glycoluril ring in the molecule and having a hydrosilyl group in the molecule as necessary. .
Patent Document 8 proposes an allyl glycoluril compound having 1 to 3 allyl groups in the molecule.
一方、グリコールウリル化合物と同様に、構造中に尿素結合（-(R)N-C(=O)-N(R)-）を含むイソシアヌレート化合物が知られているが、特許文献９には、トリス（Ｎ−２−アミノメチル）イソシアヌレート、トリス（Ｎ−２−アミノエチル）イソシアヌレート、トリス（Ｎ−２−アミノプロピル）イソシアヌレート等のトリス（Ｎ−２−アミノアルキル）イソシアヌレートが開示されている。
また、グリコールウリル環中の尿素系窒素に、アルキレン鎖を介してアミノ基を結合させる手法に関連して、特許文献１０には、イソシアヌレート環中の尿素系窒素にアルキレン鎖を介して結合したシアノ基を、水素還元してアミノ基に変換する例が開示されている（反応スキーム（Ａ）参照）。
特許文献１１には、ビスシアノエチルイソシアヌレートがビスアミノプロピルイソシアヌレートの合成原料として有用である点が開示されている。
On the other hand, an isocyanurate compound containing a urea bond (— (R) NC (═O) —N (R) —) in the structure is known as in the case of a glycoluril compound. Tris (N-2-aminoalkyl) isocyanurates such as (N-2-aminomethyl) isocyanurate, tris (N-2-aminoethyl) isocyanurate, tris (N-2-aminopropyl) isocyanurate are disclosed ing.
In addition, in connection with a technique for binding an amino group to an urea nitrogen in a glycoluril ring via an alkylene chain, Patent Document 10 discloses binding to an urea nitrogen in an isocyanurate ring via an alkylene chain. An example in which a cyano group is reduced to an amino group by hydrogen reduction is disclosed (see reaction scheme (A)).
Patent Document 11 discloses that biscyanoethyl isocyanurate is useful as a raw material for synthesizing bisaminopropyl isocyanurate.
本発明は、アミノ基を有するグリコールウリル化合物を提供することを目的とする。また、このグリコールウリル化合物の合成方法および、このグリコールウリル化合物を成分とするエポキシ樹脂用硬化剤を提供することを目的とする。 An object of the present invention is to provide a glycoluril compound having an amino group. Moreover, it aims at providing the synthesis | combining method of this glycoluril compound, and the hardening | curing agent for epoxy resins which uses this glycoluril compound as a component.
本発明者は、前記の課題を解決するために鋭意研究を重ねた結果、１，３，４，６−テトラキス（シアノアルキル）グリコールウリル化合物を還元、即ち、該グリコールウリル化合物が有するシアノ基を還元してアミノ基に変換することにより、所期の目的を達成し得ることを認め、本発明を完成するに至ったものである。
即ち、第１の発明は、化学式（I）で示される１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物である。
As a result of intensive studies to solve the above problems, the present inventor reduced 1,3,4,6-tetrakis (cyanoalkyl) glycoluril compound, that is, the cyano group contained in the glycoluril compound. It has been recognized that the intended purpose can be achieved by reduction and conversion to an amino group, and the present invention has been completed.
That is, the first invention is a 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound represented by the chemical formula (I).
第２の発明は、化学式（II）で示される１，３，４，６−テトラキス（シアノアルキル）グリコールウリル化合物が有するシアノ基を還元してアミノ基に変換することを特徴とする第1の発明の１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物の合成方法である。 A second invention is characterized in that the 1,3,4,6-tetrakis (cyanoalkyl) glycoluril compound represented by the chemical formula (II) has a cyano group reduced and converted to an amino group. It is a synthesis method of the 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound of the invention.
第３の発明は、第１の発明の１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物を成分とすることを特徴とするエポキシ樹脂用硬化剤である。 A third invention is an epoxy resin curing agent comprising the 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound of the first invention as a component.
本発明の１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物は４官能性であるので、エポキシ樹脂の硬化剤として使用することにより、従来の２官能性や３官能性の硬化剤を使用する場合に比べて、エポキシ樹脂の硬化速度を速めることができ、また、架橋密度の高い硬化物、即ち、硬度、密着性、耐熱性、耐湿性等に優れた硬化物が得られることが期待される。 Since the 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound of the present invention is tetrafunctional, by using it as a curing agent for epoxy resins, conventional bifunctional or trifunctional curing agents can be used. Compared with the case of using the epoxy resin, the curing rate of the epoxy resin can be increased, and a cured product having a high crosslinking density, that is, a cured product excellent in hardness, adhesion, heat resistance, moisture resistance, etc. can be obtained. There is expected.
本発明の１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物（以下、単に本発明のグリコールウリル化合物と云うことがある）は、前記の化学式（I）で示されるとおり、グリコールウリル環中の４つの尿素系窒素に、アルキレン鎖を介してアミノ基が結合した構造を具備する。 The 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound of the present invention (hereinafter sometimes simply referred to as the glycoluril compound of the present invention) is a glycoluril as represented by the chemical formula (I). It has a structure in which an amino group is bonded to four urea nitrogen atoms in the ring via an alkylene chain.
このグルコールウリル化合物の例としては、
１，３，４，６−テトラキス（２−アミノエチル）グリコールウリル、
１，３，４，６−テトラキス（３−アミノプロピル）グリコールウリル、
１，３，４，６−テトラキス（４−アミノブチル）グリコールウリル、
１，３，４，６−テトラキス（５−アミノペンチル）グリコールウリル、
１，３，４，６−テトラキス（２−アミノエチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（３−アミノプロピル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（４−アミノブチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（５−アミノペンチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（２−アミノエチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（３−アミノプロピル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（４−アミノブチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（５−アミノペンチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（２−アミノエチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（３−アミノプロピル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（４−アミノブチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（５−アミノペンチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（２−アミノエチル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（３−アミノプロピル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（４−アミノブチル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（５−アミノペンチル）−３ａ，６ａ−ジフェニルグリコールウリル等を挙げることができる。
As an example of this glycoluril compound,
1,3,4,6-tetrakis (2-aminoethyl) glycoluril,
1,3,4,6-tetrakis (3-aminopropyl) glycoluril,
1,3,4,6-tetrakis (4-aminobutyl) glycoluril,
1,3,4,6-tetrakis (5-aminopentyl) glycoluril,
1,3,4,6-tetrakis (2-aminoethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (3-aminopropyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (4-aminobutyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (5-aminopentyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (2-aminoethyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (3-aminopropyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (4-aminobutyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (5-aminopentyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (2-aminoethyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (3-aminopropyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (4-aminobutyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (5-aminopentyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (2-aminoethyl) -3a, 6a-diphenylglycoluril,
1,3,4,6-tetrakis (3-aminopropyl) -3a, 6a-diphenylglycoluril,
1,3,4,6-tetrakis (4-aminobutyl) -3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetrakis (5-aminopentyl) -3a, 6a-diphenylglycoluril.
本発明のグリコールウリル化合物は、その前駆体となる１，３，４，６−テトラキス（シアノアルキル）グリコールウリル化合物を還元、即ち、このグリコールウリル化合物が有するシアノ基をアミノ基に還元（変換）することにより合成することができる（反応スキーム（Ｂ）参照）。
なお、前駆体の１，３，４，６−テトラキス（シアノアルキル）グリコールウリル化合物は、前述の特許文献３に記載の方法に準じて合成することができる。
この還元反応においては、還元剤として水素を使用することが好ましく、還元反応を促進する為に触媒（イ）を使用することが好ましい。また、還元反応を円滑に進める為に、反応溶媒（ロ）を使用することが好ましい。
The glycoluril compound of the present invention reduces the 1,3,4,6-tetrakis (cyanoalkyl) glycoluril compound that is a precursor thereof, that is, reduces (converts) the cyano group of the glycoluril compound to an amino group. Can be synthesized (see Reaction Scheme (B)).
The
In this reduction reaction, it is preferable to use hydrogen as a reducing agent, and it is preferable to use a catalyst (a) in order to promote the reduction reaction. Moreover, in order to advance a reductive reaction smoothly, it is preferable to use a reaction solvent (b).
前記の１，３，４，６−テトラキス（シアノアルキル）グリコールウリル化合物としては、例えば、
１，３，４，６−テトラキス（シアノメチル）グリコールウリル、
１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル、
１，３，４，６−テトラキス（３−シアノプロピル）グリコールウリル、
１，３，４，６−テトラキス（４−シアノブチル）グリコールウリル、
１，３，４，６−テトラキス（シアノメチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（２−シアノエチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（３−シアノプロピル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（４−シアノブチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（シアノメチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（２−シアノエチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（３−シアノプロピル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（４−シアノブチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（シアノメチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（２−シアノエチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（３−シアノプロピル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（４−シアノブチル）−３ａ−フェニルグリコールウリル、
１，３，４，６−テトラキス（シアノメチル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（２−シアノエチル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（３−シアノプロピル）−３ａ，６ａ−ジフェニルグリコールウリル、
１，３，４，６−テトラキス（４−シアノブチル）−３ａ，６ａ−ジフェニルグリコールウリル等を挙げることができる。
Examples of the 1,3,4,6-tetrakis (cyanoalkyl) glycoluril compound include:
1,3,4,6-tetrakis (cyanomethyl) glycoluril,
1,3,4,6-tetrakis (2-cyanoethyl) glycoluril,
1,3,4,6-tetrakis (3-cyanopropyl) glycoluril,
1,3,4,6-tetrakis (4-cyanobutyl) glycoluril,
1,3,4,6-tetrakis (cyanomethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (2-cyanoethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (3-cyanopropyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (4-cyanobutyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (cyanomethyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (2-cyanoethyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (3-cyanopropyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (4-cyanobutyl) -3a, 6a-dimethylglycoluril,
1,3,4,6-tetrakis (cyanomethyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (2-cyanoethyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (3-cyanopropyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (4-cyanobutyl) -3a-phenylglycoluril,
1,3,4,6-tetrakis (cyanomethyl) -3a, 6a-diphenylglycoluril,
1,3,4,6-tetrakis (2-cyanoethyl) -3a, 6a-diphenylglycoluril,
1,3,4,6-tetrakis (3-cyanopropyl) -3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetrakis (4-cyanobutyl) -3a, 6a-diphenylglycoluril.
前記の触媒（イ）としては、例えば、
ラネーニッケル、ラネーコバルト、ラネー銅等のラネー触媒や、パラジウム、白金、ロジウム、ルテニウムなどの触媒金属を炭素等の担体に担持した担持触媒が挙げられる。
Examples of the catalyst (A) include:
Examples include Raney catalysts such as Raney nickel, Raney cobalt, Raney copper, and supported catalysts in which a catalytic metal such as palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon.
前記の反応溶媒（ロ）としては、例えば、
水、メタノール、エタノール、プロパノール、２−プロパノール、ブタノール、テトラヒドロフラン、ジオキサン、アセトニトリル、ベンゼン、トルエン、キシレン、ジクロロメタン、クロロホルム、四塩化炭素、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルリン酸トリアミド等の溶剤が挙げられ、その適宜量を使用することができる。
なお、これらから選択される２種以上を組み合わせて、使用してもよい。
As the reaction solvent (b), for example,
Water, methanol, ethanol, propanol, 2-propanol, butanol, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, etc. Solvents can be mentioned and appropriate amounts thereof can be used.
In addition, you may use combining 2 or more types selected from these.
この還元反応において、還元剤として水素を使用する場合には、反応系（反応容器）内に水素が存在すればよいが、反応系内における水素圧を、０．１〜２０ＭＰａの範囲に設定することが好ましい。
また、この還元反応の反応温度は、０〜１５０℃の範囲に設定されることが好ましく、同反応時間は、前記の反応温度に応じて適宜設定されるが、１〜４８時間の範囲に設定されることが好ましい。
In this reduction reaction, when hydrogen is used as a reducing agent, it suffices if hydrogen is present in the reaction system (reaction vessel). It is preferable.
The reaction temperature of this reduction reaction is preferably set in the range of 0 to 150 ° C., and the reaction time is appropriately set according to the reaction temperature, but is set in the range of 1 to 48 hours. It is preferred that
この反応の終了後、得られた反応混合物から、例えば、溶媒抽出法等の手段によって、目的物である本発明のグリコールウリル化合物を取り出すことができる。
更に、必要により、水等による洗浄や、活性炭処理、シリカゲルクロマトグラフィー等の手段を利用して精製することができる。
After the completion of this reaction, the glycoluril compound of the present invention, which is the target product, can be taken out of the obtained reaction mixture by means such as solvent extraction.
Furthermore, it can be purified using means such as washing with water, activated carbon treatment, silica gel chromatography, etc., if necessary.
本発明のグリコールウリル化合物は、活性水素を有するアミノ基（-NH2）を４つ有し、所謂ポリアミン類（化合物）に分類される物質である。
アミン類をエポキシ化合物に接触させると、エポキシ化合物は重付加型の反応によって重合が進行し、硬化物（重合物）を生成するところから、アミン類はエポキシ樹脂用硬化剤の一成分として広く使用されている。中でもポリアミン類には、一般的なアミン類とは異なって、特徴的な硬化作用が期待される。
本発明のグリコールウリル化合物は、分子中において、アミノ基が立体的に特定の距離間隔で位置（分布）し、且つ、対称性の高い構造を具備しているので、従来知られたポリアミン型のエポキシ樹脂用硬化剤に匹敵して、或いは更に優れて、特徴的な硬化作用を発揮することが期待される。
The glycoluril compound of the present invention has four amino groups (—NH 2 ) having active hydrogen, and is classified into so-called polyamines (compounds).
When amines are brought into contact with an epoxy compound, the polymerization of the epoxy compound proceeds by a polyaddition-type reaction to produce a cured product (polymer), so amines are widely used as a component of a curing agent for epoxy resins. Has been. In particular, polyamines are expected to have a characteristic curing action unlike general amines.
In the glycoluril compound of the present invention, amino groups are sterically positioned (distributed) at specific distance intervals in the molecule and have a highly symmetric structure. It is expected to exhibit a characteristic curing action comparable to or better than a curing agent for epoxy resins.
本発明のグリコールウリル化合物を成分とするエポキシ樹脂用硬化剤は、必要により、公知のエポキシ樹脂用の硬化剤や、同硬化促進剤と併用されて、エポキシ化合物（エポキシ樹脂と称されることがある）に配合されて、エポキシ樹脂組成物が調製（製造）される。 The epoxy resin curing agent containing the glycoluril compound of the present invention as a component is used in combination with a known epoxy resin curing agent or curing accelerator, if necessary, to be referred to as an epoxy compound (epoxy resin). The epoxy resin composition is prepared (manufactured).
前記のエポキシ化合物としては、グリシジルエーテル型、グリシジルエステル型、グリシジルアミン型、酸化型等のエポキシ化合物が挙げられる。
グリシジルエーテル型としては、Ｂｉｓ−Ａ型エポキシ化合物、Ｂｉｓ−Ｆ型エポキシ化合物、Ｈｉｇｈ−Ｂｒ型エポキシ化合物、ノボラック型エポキシ化合物、アルコール型エポキシ化合物、脂肪族型エポキシ化合物（例えば、１，４−ブタンジグリシジルエーテル）が挙げられる。
グリシジルエステル型としては、ヒドロフタル酸型エポキシ化合物、ダイマー酸型エポキシ化合物が挙げられる。
グリシジルアミン型としては、芳香族アミン型エポキシ化合物、アミノフェノール型エポキシ化合物が挙げられる。
酸化型としては、脂環型エポキシ化合物が挙げられる。
Examples of the epoxy compound include glycidyl ether type, glycidyl ester type, glycidyl amine type, and oxidized type epoxy compounds.
Examples of the glycidyl ether type include a Bis-A type epoxy compound, a Bis-F type epoxy compound, a High-Br type epoxy compound, a novolac type epoxy compound, an alcohol type epoxy compound, and an aliphatic type epoxy compound (for example, 1,4-butane). Diglycidyl ether).
Examples of the glycidyl ester type include hydrophthalic acid type epoxy compounds and dimer acid type epoxy compounds.
Examples of the glycidylamine type include aromatic amine type epoxy compounds and aminophenol type epoxy compounds.
An alicyclic epoxy compound is mentioned as an oxidation type.
前記の公知のエポキシ樹脂用の硬化剤としては、脂肪族ポリアミン類、脂環式ポリアミン類、芳香族ポリアミン類や特殊ポリアミン類を挙げることができる。
脂肪族ポリアミン類としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ｍ−キシレンジアミン、ヘキサメチレンジアミン、トリメチルヘキサメチレンジアミン、２−メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン等が挙げられる。
脂環式ポリアミン類としては、イソフォロンジアミン、１，３−ビスアミノメチルシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２−ジアミノシクロヘキサン、ビス（４−アミノ−３−メチルシクロヘキシル）メタン等が挙げられる。
芳香族ポリアミン類としては、ジアミノジフェニルメタン、ｍ−フェニレンジアミン、ジアミノジフェニルスルホン等が挙げられる。
特殊ポリアミン類としては、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、ポリシクロヘキシルポリアミン混合物、３，９−ビス（３−アミノプロピル）−２，４，５，１０−テトラスピロ［５．５］ウンデカン、Ｎ−アミノエチルピペラジン等が挙げられる。
Examples of the known curing agent for epoxy resins include aliphatic polyamines, alicyclic polyamines, aromatic polyamines and special polyamines.
Examples of the aliphatic polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine and the like.
The alicyclic polyamines include isophorone diamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl). ) Methane and the like.
Aromatic polyamines include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone and the like.
Special polyamines include polyoxypropylene diamine, polyoxypropylene triamine, polycyclohexyl polyamine mixture, 3,9-bis (3-aminopropyl) -2,4,5,10-tetraspiro [5.5] undecane, N -Aminoethyl piperazine etc. are mentioned.
前記の公知のエポキシ樹脂用の硬化促進剤としては、脂肪酸類、安息香酸類、アルコール類、フェノール類、メルカプト類等を挙げることができる。
なお、「エポキシ樹脂技術協会編，総説エポキシ樹脂，第１巻，基礎編Ｉ，２００３年」に記載されたエポキシ樹脂用の硬化剤および同硬化促進剤は、引用により、本明細書の開示に含む。
Examples of the known curing accelerator for epoxy resins include fatty acids, benzoic acids, alcohols, phenols, mercapts and the like.
In addition, the curing agent and the curing accelerator for epoxy resin described in “Epoxy Resin Technical Association, Review Epoxy Resin,
前記のエポキシ樹脂組成物は、必要により、
顔料（チタン白、シアニンブルー、ウォッチングレッド、ベンガラ、カーボンブラック、アニリンブラック、マンガンブルー、鉄黒、ウルトラマリンブルー、ハンザレッド、クロームイエロー、クロームグリーン等）、
無機充填剤（炭酸カルシウム、カオリン、クレー、タルク、マイカ、硫酸バリウム、リトポン、石コウ、ステアリン酸亜鉛、パーライト、石英、石英ガラス、溶融シリカ、球状シリカ等のシリカ粉等、球状アルミナ、破砕アルミナ、酸化マグネシウム、酸化ベリリウム、酸化チタン等の酸化物類、窒化ホウ素、窒化ケイ素、窒化アルミニウム等の窒化物類、炭化ケイ素等の炭化物類、水酸化アルミニウム、水酸化マグネシウム等の水酸化物類、銅、銀、鉄、アルミニウム、ニッケル、チタン等の金属類や合金類、ダイヤモンド、カーボン等の炭素系材料等）、
熱可塑性樹脂および熱硬化性樹脂（高密度、中密度、低密度の各種ポリエチレン、ポリプロピレン、ポリブテン、ポリペンテン等の単独重合体、エチレン−プロピレン共重合体、ナイロン−６、ナイロン−６，６等のポリアミド系樹脂、塩化ビニル系樹脂、ニトロセルロース系樹脂、塩化ビニリデン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、スチレン系樹脂、ビニルエステル系樹脂、ポリエステル系樹脂、フェノール樹脂（フェノール化合物）、シリコーン系樹脂、フッ素系樹脂、アクリルゴムやウレタンゴムなどの各種エラストマー樹脂、メタクリル酸メチル−ブタジエン−スチレン系グラフト共重合体やアクリロニトリル−ブタジエン−スチレン系グラフト共重合体などのグラフト共重合体等）、
補強剤（ガラス繊維、炭素繊維等）、
垂れ止め剤（水添ヒマシ油、微粒子無水硅酸等）、
艶消し剤（微粉シリカ、パラフィンワックス等）、
研削剤（ステアリン酸亜鉛等）、
内部離型剤（ステアリン酸等の脂肪酸、ステアリン酸カルシウムの脂肪酸金属塩、ステアリン酸アミド等の脂肪酸アミド、脂肪酸エステル、ポリオレフィンワックス、パラフィンワックス等）、
界面活性剤、レベリング剤、消泡剤、粘度調整用希釈剤（有機溶剤）、カップリング剤、香料、難燃化剤などの添加剤（改質剤）を含有してもよい。
The above epoxy resin composition is, if necessary,
Pigments (titanium white, cyanine blue, watching red, bengara, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.)
Inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, stone kow, zinc stearate, perlite, quartz, quartz glass, fused silica, spherical silica, etc., spherical alumina, crushed alumina , Oxides such as magnesium oxide, beryllium oxide and titanium oxide, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, Metals such as copper, silver, iron, aluminum, nickel, titanium and alloys, carbon-based materials such as diamond and carbon),
Thermoplastic resins and thermosetting resins (high density, medium density, low density polyethylene, polypropylene, polybutene, polypentene and other homopolymers, ethylene-propylene copolymers, nylon-6, nylon-6, 6 etc. Polyamide resin, vinyl chloride resin, nitrocellulose resin, vinylidene chloride resin, acrylic resin, acrylamide resin, styrene resin, vinyl ester resin, polyester resin, phenol resin (phenol compound), silicone resin , Fluororesins, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers),
Reinforcing agent (glass fiber, carbon fiber, etc.),
Anti-sagging agents (hydrogenated castor oil, fine succinic anhydride, etc.)
Matting agent (fine silica, paraffin wax, etc.),
Abrasives (such as zinc stearate),
Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearamide, fatty acid esters, polyolefin wax, paraffin wax, etc.)
You may contain additives (modifiers), such as surfactant, a leveling agent, an antifoamer, a viscosity adjustment diluent (organic solvent), a coupling agent, a fragrance | flavor, and a flame retardant.
本発明のエポキシ樹脂用硬化剤を配合したエポキシ樹脂組成物は、土木建築用接着剤、半導体用封止剤、プリント回路基板や高圧電力用モールド機器用等の絶縁材、缶用や自動車用等の塗料等に好適である。 The epoxy resin composition containing the curing agent for epoxy resin of the present invention is an adhesive for civil engineering and construction, a sealing agent for semiconductors, an insulating material for printed circuit boards and molded devices for high voltage power, for cans, for automobiles, etc. It is suitable for coating materials and the like.
以下、実施例および比較例により、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
なお、実施例および比較例において使用した主原料は、以下のとおりである。
Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these.
The main raw materials used in the examples and comparative examples are as follows.
［主原料］
・１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル：前述の特許文献３に記載された方法に準拠して合成した。
・ラネー触媒：スポンジコバルト（展開コバルト）、川研ファインケミカル社製、品名「ＯＤＨＴ−６０」
・エポキシ化合物：１，４−ブタンジグリシジルエーテル、和光純薬工業社製
・エポキシ樹脂用硬化剤：ヘキサメチレンジアミン、和光純薬工業社製
[Main ingredients]
1,3,4,6-tetrakis (2-cyanoethyl) glycoluril: synthesized according to the method described in Patent Document 3 above.
Raney catalyst: sponge cobalt (expanded cobalt), manufactured by Kawaken Fine Chemical Co., Ltd., “ODHT-60”
-Epoxy compound: 1,4-butanediglycidyl ether, manufactured by Wako Pure Chemical Industries, Ltd.- Curing agent for epoxy resin: hexamethylene diamine, manufactured by Wako Pure Chemical Industries, Ltd.
〔実施例１〕
＜１，３，４，６−テトラキス（３−アミノプロピル）グリコールウリルの合成＞
容量１０００ｍｌのオートクレーブに、１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル１７．７２ｇ（５０．０ｍｍｏｌ）、ラネー触媒０．５９ｇ（１０．０ｍｍｏｌ）、２−プロパノール２００．００ｇを仕込み、オートクレーブの内部（反応曹内）を水素置換した。
次いで、１００℃にて５時間撹拌し、得られた反応混合物から不溶解分をろ別し、続いて濃縮することにより、生成物として、１７．８４ｇの黄色液体を得た（収率：９６．３％）。
[Example 1]
<Synthesis of 1,3,4,6-tetrakis (3-aminopropyl) glycoluril>
Into an autoclave with a capacity of 1000 ml, 17,72 g (50.0 mmol) of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril, 0.59 g (10.0 mmol) of Raney catalyst and 200.00 g of 2-propanol were charged. The inside of the autoclave (within the reaction soda) was replaced with hydrogen.
Subsequently, the mixture was stirred at 100 ° C. for 5 hours, and the insoluble matter was filtered off from the obtained reaction mixture, followed by concentration to obtain 17.84 g of a yellow liquid as a product (yield: 96 .3%).
この黄色液体の１Ｈ−ＮＭＲスペクトルデータは、以下のとおりであった。
・1H-NMR (d6-DMSO) δ: 5.31(s, 2H), 3.44(ddd, 4H), 3.11(ddd, 4H), 2.49(t, 8H), 1.56(m, 8H), 1.52(s, 8H).
また、この黄色液体のＩＲスペクトルデータは、図１に示したチャートのとおりであった。
これらのスペクトルデータより、得られた黄色液体は、化学式（I-1）で示される表題のグリコールウリル化合物であるものと同定した。
The 1 H-NMR spectrum data of this yellow liquid was as follows.
・1 H-NMR (d 6 -DMSO) δ: 5.31 (s, 2H), 3.44 (ddd, 4H), 3.11 (ddd, 4H), 2.49 (t, 8H), 1.56 (m, 8H), 1.52 ( s, 8H).
The IR spectrum data of this yellow liquid was as shown in the chart shown in FIG.
From these spectral data, the obtained yellow liquid was identified as the title glycoluril compound represented by the chemical formula (I-1).
[実施例２]
実施例１において合成した１，３，４，６−テトラキス（３−アミノプロピル）グリコールウリル１．８５ｇ（５．０ｍｍｏｌ）と、１，４−ブタンジグリシジルエーテル４．０５ｇ（２０．０ｍｍｏｌ）を混合した。
得られた混合物（液状物）を２５℃にて静置し、目視および触感により混合物の硬化の様子を観察したところ、混合物が硬化するまでに要した時間は５分であった。
[Example 2]
1,3,4,6-tetrakis (3-aminopropyl) glycoluril 1.85 g (5.0 mmol) synthesized in Example 1 and 4.05 g (20.0 mmol) of 1,4-butanediglycidyl ether Mixed.
The obtained mixture (liquid material) was allowed to stand at 25 ° C., and the curing of the mixture was observed visually and tactilely. As a result, the time required for the mixture to cure was 5 minutes.
[比較例１]
１，３，４，６−テトラキス（３−アミノプロピル）グリコールウリルの代わりに、ヘキサメチレンジアミン１．１６ｇ（１０．０ｍｍｏｌ）を使用した以外は、実施例２と同様にして混合物（液状物）を調製し、得られた混合物の硬化の様子を観察したところ、混合物が硬化するまでに要した時間は３０分であった。
[Comparative Example 1]
A mixture (liquid) in the same manner as in Example 2 except that 1.16 g (10.0 mmol) of hexamethylenediamine was used instead of 1,3,4,6-tetrakis (3-aminopropyl) glycoluril. When the state of hardening of the obtained mixture was observed, the time required for the mixture to harden was 30 minutes.
本発明の１，３，４，６−テトラキス（アミノアルキル）グリコールウリル化合物は、エポキシ樹脂の硬化剤としての利用が期待されるので、本発明の産業上の利用可能性は多大である。
Since the 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound of the present invention is expected to be used as a curing agent for epoxy resins, the industrial applicability of the present invention is great.
Claims (3)
A curing agent for an epoxy resin comprising the 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound according to claim 1 as a component.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52123428A (en) * | 1976-04-08 | 1977-10-17 | American Cyanamid Co | Polymerizing* particulate paint composite |
| JPH11171887A (en) * | 1997-12-12 | 1999-06-29 | Shikoku Chem Corp | 1,3,4,6-tetraallyl glycoluril compound and synthesis of the same compound |
| JPH11180963A (en) * | 1997-12-24 | 1999-07-06 | Shikoku Chem Corp | Production of bis(cyanoethyl)isocyanurate |
| JP2005527398A (en) * | 2002-03-01 | 2005-09-15 | マーケム コーポレイション | Marking substrate |
| JP2014058452A (en) * | 2012-09-14 | 2014-04-03 | Shikoku Chem Corp | New isocyanurate compound |
| JP2015054843A (en) * | 2013-09-12 | 2015-03-23 | 四国化成工業株式会社 | Tetrakis(carboxyalkyl)glycolurils and application thereof |
| JP2015054856A (en) * | 2013-09-13 | 2015-03-23 | 四国化成工業株式会社 | Glycidyl glycolurils and application thereof |
| JP2015057375A (en) * | 2013-09-14 | 2015-03-26 | 四国化成工業株式会社 | Novel 1,3,4,6-tetrakis ((meth)acryloyloxy alkyl)glycoluril |
| JP2015059115A (en) * | 2013-09-20 | 2015-03-30 | 四国化成工業株式会社 | Novel allylglycolurils |
| JP2015059099A (en) * | 2013-09-18 | 2015-03-30 | 四国化成工業株式会社 | Mercaptoalkylglycolurils and use thereof |
| JP2015059101A (en) * | 2013-09-19 | 2015-03-30 | 四国化成工業株式会社 | Glycoluril ring-containing organosilane, glycoluril ring-containing organosiloxane, and methods for producing them |
-
2015
- 2015-09-30 JP JP2015192481A patent/JP6483583B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52123428A (en) * | 1976-04-08 | 1977-10-17 | American Cyanamid Co | Polymerizing* particulate paint composite |
| JPH11171887A (en) * | 1997-12-12 | 1999-06-29 | Shikoku Chem Corp | 1,3,4,6-tetraallyl glycoluril compound and synthesis of the same compound |
| JPH11180963A (en) * | 1997-12-24 | 1999-07-06 | Shikoku Chem Corp | Production of bis(cyanoethyl)isocyanurate |
| JP2005527398A (en) * | 2002-03-01 | 2005-09-15 | マーケム コーポレイション | Marking substrate |
| JP2014058452A (en) * | 2012-09-14 | 2014-04-03 | Shikoku Chem Corp | New isocyanurate compound |
| JP2015054843A (en) * | 2013-09-12 | 2015-03-23 | 四国化成工業株式会社 | Tetrakis(carboxyalkyl)glycolurils and application thereof |
| JP2015054856A (en) * | 2013-09-13 | 2015-03-23 | 四国化成工業株式会社 | Glycidyl glycolurils and application thereof |
| JP2015057375A (en) * | 2013-09-14 | 2015-03-26 | 四国化成工業株式会社 | Novel 1,3,4,6-tetrakis ((meth)acryloyloxy alkyl)glycoluril |
| JP2015059099A (en) * | 2013-09-18 | 2015-03-30 | 四国化成工業株式会社 | Mercaptoalkylglycolurils and use thereof |
| JP2015059101A (en) * | 2013-09-19 | 2015-03-30 | 四国化成工業株式会社 | Glycoluril ring-containing organosilane, glycoluril ring-containing organosiloxane, and methods for producing them |
| JP2015059115A (en) * | 2013-09-20 | 2015-03-30 | 四国化成工業株式会社 | Novel allylglycolurils |
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