JP6512392B2 - Epoxy compound, epoxy composition and adhesive - Google Patents
Epoxy compound, epoxy composition and adhesive Download PDFInfo
- Publication number
- JP6512392B2 JP6512392B2 JP2014104455A JP2014104455A JP6512392B2 JP 6512392 B2 JP6512392 B2 JP 6512392B2 JP 2014104455 A JP2014104455 A JP 2014104455A JP 2014104455 A JP2014104455 A JP 2014104455A JP 6512392 B2 JP6512392 B2 JP 6512392B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- compound
- group
- epoxy compound
- polyhydric alcohol
- 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.)
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- 239000004593 Epoxy Substances 0.000 title claims description 135
- 150000001875 compounds Chemical class 0.000 title claims description 107
- 239000000203 mixture Substances 0.000 title claims description 39
- 239000000853 adhesive Substances 0.000 title claims description 29
- 230000001070 adhesive effect Effects 0.000 title claims description 29
- 125000003700 epoxy group Chemical group 0.000 claims description 71
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 54
- 150000005846 sugar alcohols Polymers 0.000 claims description 44
- 125000001931 aliphatic group Chemical group 0.000 claims description 31
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 20
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 19
- 229920003002 synthetic resin Polymers 0.000 description 19
- 239000000057 synthetic resin Substances 0.000 description 19
- 150000002739 metals Chemical class 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 glycidyl ether compound Chemical class 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 230000003301 hydrolyzing effect Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000600 sorbitol Substances 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 150000007514 bases Chemical class 0.000 description 7
- 238000006266 etherification reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000008234 soft water Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000001408 amides Chemical class 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
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 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
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- OTFRVOUYHSTUJC-UHFFFAOYSA-N 3-aminosilylpropan-1-amine Chemical class N[SiH2]CCCN OTFRVOUYHSTUJC-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- MYSPBSKLIFPWDI-UHFFFAOYSA-N octacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O MYSPBSKLIFPWDI-UHFFFAOYSA-N 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical class [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 125000001730 thiiranyl group Chemical group 0.000 description 1
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- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、新規なエポキシ化合物、このエポキシ化合物を含有するエポキシ組成物及び接着剤に関する。 The present invention relates to a novel epoxy compound, an epoxy composition containing the epoxy compound, and an adhesive.
従来、エポキシ化合物（エポキシ基含有化合物）は、接着性を示す化合物として良く知られており、その接着強度を向上させるべく種々の試みがなされている。
例えば、特許文献１には、極性を高めるアミン系の硬化剤を用いることが開示されており、特許文献２には、シランカップリング剤を用いた前処理を行う方法が開示されており、特許文献３には、エポキシ基含有化合物が有するオキシラン環の全部または一部をチイラン環とすることが開示されている。
Conventionally, epoxy compounds (epoxy group-containing compounds) are well known as compounds exhibiting adhesiveness, and various attempts have been made to improve the adhesive strength.
For example, Patent Document 1 discloses using an amine-based curing agent to enhance polarity, Patent Document 2 discloses a method of performing pretreatment using a silane coupling agent, and Patent Document 3 discloses that all or part of the oxirane ring possessed by the epoxy group-containing compound is a thiirane ring.
しかしながら、近年、金属や金属酸化物等の無機充填剤を高充填したエポキシ樹脂組成物等においては、少ない樹脂量でより高いレベルの接着力が求められているが、従来のエポキシ化合物では十分な性能となっていなかった。今回、本発明者等は、従来とは異なる手法でエポキシ接着剤の金属や合成樹脂との接着強度を向上させることを検討し、その結果、新規なエポキシ化合物を用いることにより金属や合成樹脂との接着強度に優れるエポキシ接着剤を提供できることを見出した。 However, in recent years, with epoxy resin compositions and the like highly filled with inorganic fillers such as metals and metal oxides, higher levels of adhesion are required with a small amount of resin, but conventional epoxy compounds are sufficient. It was not a performance. In the present study, the present inventors examined improving the adhesive strength of an epoxy adhesive with a metal or synthetic resin by a method different from the conventional method, and as a result, by using a novel epoxy compound, it is possible to It has been found that an epoxy adhesive excellent in adhesive strength can be provided.
本発明のエポキシ化合物は、ヒドロキシ化合物をグリシジルエーテル化してなる分子内に複数のエポキシ基を有する化合物の一部のエポキシ基を加水分解してなることを特徴とする。 The epoxy compound of the present invention is characterized by hydrolyzing a part of epoxy groups of a compound having a plurality of epoxy groups in a molecule formed by glycidyl etherifying a hydroxy compound.
本発明のエポキシ化合物において、上記分子内に複数のエポキシ基を有する化合物は、脂肪族多価アルコール（Ａ）又は脂肪族多価アルコール（Ａ）をエチレンオキサイド及び／又はプロピレンオキサイドで変性した脂肪族多価アルコール（Ａ´）をグリシジルエーテル化してなるものであることが好ましい。 In the epoxy compound of the present invention, the compound having a plurality of epoxy groups in the molecule is an aliphatic polyhydric alcohol (A) or an aliphatic polyhydric alcohol (A) modified with ethylene oxide and / or propylene oxide. It is preferable that it is what glycidyl-etherifies polyhydric alcohol (A ').
上記エポキシ化合物は、上記脂肪族多価アルコール（Ａ）又は脂肪族多価アルコール（Ａ）をエチレンオキサイド及び／又はプロピレンオキサイドで変性した脂肪族多価アルコール（Ａ´）をグリシジルエーテル化した際のエポキシ含量の５〜４０％に相当するエポキシ基を加水分解してなるものであることが好ましい。 The epoxy compound is obtained by glycidyl etherifying an aliphatic polyhydric alcohol (A ′) obtained by modifying the aliphatic polyhydric alcohol (A) or the aliphatic polyhydric alcohol (A) with ethylene oxide and / or propylene oxide. It is preferable to be obtained by hydrolyzing an epoxy group corresponding to 5 to 40% of the epoxy content.
上記エポキシ化合物において、上記脂肪族多価アルコール（Ａ）は、分子内に３つ以上のヒドロキシ基を有する化合物であることが好ましい。 In the epoxy compound, the aliphatic polyhydric alcohol (A) is preferably a compound having three or more hydroxy groups in the molecule.
本発明のエポキシ組成物は、本発明のエポキシ化合物を含有することを特徴とする。
また、本発明の接着剤は、本発明のエポキシ組成物を含むことを特徴とする。
The epoxy composition of the present invention is characterized by containing the epoxy compound of the present invention.
Also, the adhesive of the present invention is characterized by containing the epoxy composition of the present invention.
本発明のエポキシ化合物は、特定のエポキシ基の一部が加水分解された新規な構造を有し、金属や合成樹脂との接着強度に優れた接着剤に好適に使用することができる。
本発明のエポキシ組成物は、本発明のエポキシ化合物を含有するため、金属同士、合成樹脂同士、及び金属と合成樹脂との各接着性に優れた接着剤として好適に使用することができる。
本発明の接着剤は、本発明のエポキシ化合物を含有するため、金属同士、合成樹脂同士、及び金属と合成樹脂との各接着性に極めて優れる。
The epoxy compound of the present invention has a novel structure in which a part of a specific epoxy group is hydrolyzed, and can be suitably used for an adhesive excellent in adhesion strength to metals and synthetic resins.
Since the epoxy composition of the present invention contains the epoxy compound of the present invention, it can be suitably used as an adhesive excellent in adhesion between metals, between synthetic resins, and between metal and synthetic resin.
Since the adhesive of the present invention contains the epoxy compound of the present invention, it is extremely excellent in the adhesion between metals, between synthetic resins, and between metal and synthetic resin.
まず、本発明のエポキシ化合物について説明する。
本発明のエポキシ化合物は、分子内に複数のエポキシ基を有する化合物の一部のエポキシ基を加水分解してなるものであり、分子内に複数のエポキシ基を有する化合物は、ヒドロキシ化合物をグリシジルエーテル化してなるものである。
ここで、上記ヒドロキシ化合物は、それ自身がエポキシ基を有する場合には少なくとも１つのヒドロキシ基を有するものであればよく、それ自身がエポキシ基を有していない場合には２つ以上のヒドロキシ基を有するものである。
First, the epoxy compound of the present invention will be described.
The epoxy compound of the present invention is formed by hydrolysis of a part of epoxy groups of a compound having a plurality of epoxy groups in the molecule, and the compound having a plurality of epoxy groups in the molecule is a hydroxy compound glycidyl ether It is a matter of
Here, the above-mentioned hydroxy compound may be one having at least one hydroxy group when it itself has an epoxy group, and two or more hydroxy groups when it does not have an epoxy group itself. The
ヒドロキシ化合物をグリシジルエーテル化してなる分子内に複数のエポキシ基を有する化合物の具体例としては、例えば、ビスフェノールＡ型エポキシ、ビスフェノールＦ型エポキシ、ビスフェノールＥ型エポキシ、フェノールノボラック型エポキシ、クレゾールノボラック型エポキシ等が挙げられ、また、ビスフェノールＡ型エポキシ、ビスフェノールＦ型エポキシ、ビスフェノールＥ型エポキシ、フェノールノボラック型エポキシ、クレゾールノボラック型エポキシ等のうち２級のヒドロキシ基を有するものを出発材料として、その２級のヒドロキシ基にグリシジル基が導入されたもの（グリシジルエーテル化されたもの）等も挙げられる。
また、下記一般式（１）〜（３）に示される芳香族化合物のいずれかを出発原料として、グリシジル基が導入された化合物等も挙げられる。
Specific examples of the compound having a plurality of epoxy groups in the molecule formed by glycidyl etherifying a hydroxy compound include, for example, bisphenol A epoxy, bisphenol F epoxy, bisphenol E epoxy, phenol novolac epoxy, cresol novolac epoxy And the like, and, among bisphenol A type epoxy, bisphenol F type epoxy, bisphenol E type epoxy, phenol novolac type epoxy, cresol novolac type epoxy and the like, those having a secondary hydroxyl group as a starting material, secondary thereof And those having a glycidyl group introduced into the hydroxy group of the above (glycidyl etherified), and the like are also mentioned.
Moreover, the compound etc. by which the glycidyl group was introduce | transduced are also mentioned by making any of the aromatic compound shown by following General formula (1)-(3) into a starting material.
（式中、Ｒ１〜Ｒ６のうち、少なくとも２つはヒドロキシ基であり、残りはそれぞれ独立して、水素原子、アルキル基、アルケニル基又はアラルキル基である。） (In the formula, at least two of R 1 to R 6 are hydroxy groups, and the rest are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group.)
（式中、Ｒ７〜Ｒ１４のうち、少なくとも２つはヒドロキシ基であり、残りはそれぞれ独立して、水素原子、アルキル基、アルケニル基又はアラルキル基である。） (In the formula, at least two of R 7 to R 14 are hydroxy groups, and the rest are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group.)
（式中、Ｒ１５〜Ｒ２４のうち、少なくとも２つはヒドロキシ基であり、残りはそれぞれ独立して、水素原子、アルキル基、アルケニル基又はアラルキル基である。） (In the formula, at least two of R 15 to R 24 are hydroxy groups, and the rest are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group.)
ヒドロキシ化合物をグリシジルエーテル化してなる分子内に複数のエポキシ基を有する化合物は、脂肪族多価アルコール（Ａ）をグリシジルエーテル化してなるものが好ましい。
エポキシ基を加水分解する際に、加水分解反応で使用する水との親和性が高く、反応を効率よく進められるからである。
The compound having a plurality of epoxy groups in the molecule formed by glycidyl etherifying a hydroxy compound is preferably one formed by glycidyl etherifying an aliphatic polyhydric alcohol (A).
This is because, when the epoxy group is hydrolyzed, the affinity with water used in the hydrolysis reaction is high, and the reaction can be efficiently advanced.
上記ヒドロキシ化合物をグリシジルエーテル化する方法としては特に限定されず、例えば、ルイス酸触媒の存在下、ヒドロキシ化合物のヒドロキシ基１モルに対し、エピハロヒドリン類０．３〜２．０モルを反応させ、引き続き、ヒドロキシ化合物のヒドロキシ基１モルに対し、０．５〜２．０モルの塩基性化合物を作用させる方法、ヒドロキシ化合物のヒドロキシ基１モルに対し、エピハロヒドリン類０．３〜２０モルを添加し、この混合物に、上記ヒドロキシ化合物のヒドロキシ基１モルに対し０．９〜２．０モルの塩基性化合物を一括添加または徐々に添加しながら反応させる方法等が挙げられる。
また、例えば、ヒドキシ化合物をアリルエーテル化した後、アリル基を酸化せしめてグリシジルエーテル化合物を得る方法も、ヒドロキシ化合物をグリシジルエーテル化する方法として用いることができる。
The method for glycidyl etherifying the above hydroxy compound is not particularly limited. For example, in the presence of a Lewis acid catalyst, 0.3 to 2.0 moles of epihalohydrins are reacted with 1 mole of hydroxy group of the hydroxy compound, and subsequently (A) 0.5 to 2.0 moles of a basic compound is allowed to act on 1 mole of the hydroxy group of the hydroxy compound, and 0.3 to 20 moles of an epihalohydrin is added to 1 mole of the hydroxy group of the hydroxy compound, The method of making it react, adding 0.9-2.0 mol of basic compounds to this mixture at once with or gradually adding with respect to 1 mol of hydroxy groups of the said hydroxy compound etc. is mentioned.
Also, for example, a method of obtaining a glycidyl ether compound by oxidizing an allyl group after allyl etherification of a hydroxy compound can also be used as a method of glycidyl etherifying a hydroxy compound.
上記塩基性化合物は固形で使用しても、その水溶液で使用してもよく、水溶液を使用する場合は、連続的に添加すると共に、反応混合物中から減圧下又は常圧下、連続的に水及びエピハロヒドリン類を留出させ、更に分液して水は除去しエピハロヒドリン類は反応混合物中に連続的に戻してもよい。 The above basic compound may be used as a solid or as an aqueous solution thereof, and when an aqueous solution is used, it is continuously added, and from the reaction mixture, water and continuously under reduced pressure or under normal pressure. The epihalohydrins may be distilled and further separated to remove water, and the epihalohydrins may be continuously returned to the reaction mixture.
上記エピハロヒドリン類としては特に限定されないが、例えば、エピクロルヒドリン、エピブロモヒドリン等が挙げられる。なかでも入手が容易なことからエピクロルヒドリンが好ましい。 The epihalohydrins are not particularly limited, and examples thereof include epichlorohydrin and epibromohydrin. Among these, epichlorohydrin is preferable because of easy availability.
上記塩基性化合物としては特に限定されないが、例えば、アルカリ土類金属水酸化物、アルカリ金属炭酸塩、アルカリ金属水酸化物等が挙げられる。特に、グリシジルエーテル化によりエポキシ基を導入する反応の活性に優れる点からアルカリ金属水酸化物が好ましい。上記アルカリ金属水酸化物としては、例えば、水酸化ナトリウム、水酸化カリウム等が挙げられる。
ここで、アルカリ金属水酸化物は、濃度１０〜５５重量％程度の水溶液の形態で使用してもよいし、固形の形態で使用しても構わない。
The basic compound is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred in terms of excellent activity of the reaction for introducing an epoxy group by glycidyl etherification. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
Here, the alkali metal hydroxide may be used in the form of an aqueous solution having a concentration of about 10 to 55% by weight, or may be used in the form of solid.
ヒドロキシ化合物をグリシジルエーテル化する反応においては、反応を促進させることを目的に、反応触媒として、例えば、４級アンモニウム塩類、３級アミン類、ホスホニウム塩類、ホスフィン類等を添加してもよい。
上記反応触媒は、ヒドロキシル基に対して、０．０１〜１０モル％程度使用することが好ましい。
In the reaction of glycidyl etherifying a hydroxy compound, for example, quaternary ammonium salts, tertiary amines, phosphonium salts, phosphines and the like may be added as reaction catalysts for the purpose of promoting the reaction.
It is preferable to use the said reaction catalyst about 0.01-10 mol% with respect to a hydroxyl group.
また、上記グリシジルエーテル化を行う際には、有機溶媒を併用してもよい。反応速度を高めることができるからである。
上記有機溶媒としては特に限定されず、例えば、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール、１−プロピルアルコール、イソプロピルアルコール、１−ブタノール、セカンダリーブタノール、ターシャリーブタノール等のアルコール類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類、テトラヒドロフラン、１，４−ジオキサン、１，３−ジオキサン、ジエトキシエタン等のエーテル類、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、それぞれ単独で使用しても良く、２種以上を併用してもよい。
Moreover, when performing the said glycidyl etherification, you may use an organic solvent together. It is because reaction speed can be raised.
The organic solvent is not particularly limited, and examples thereof include ketones such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, alcohols such as secondary butanol and tertiary butanol, methyl cellosolve, Cellosolves such as ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane and the like, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.
上記脂肪族多価アルコール（Ａ）としては、分子内に複数のヒドロキシ基を有するものであれば特に限定されないが、分子内に３つ以上のヒドロキシ基を有するものが好ましい。
本発明のエポキシ化合物は、エポキシ基と加水分解されたエポキシ基に由来するヒドロキシ基とを有する化合物であるが、脂肪族多価アルコール（Ａ）として分子内に３つ以上のヒドロキシ基を有するものを用いると、脂肪族多価アルコール（Ａ）をグリシジルエーテル化した後、エポキシ基の一部を加水分解した際に確実にエポキシ基の一部のみ加水分解し、エポキシ化合物内にエポキシ基と加水分解されたエポキシ基に由来するヒドロキシ基を共存させることができるからである。
The aliphatic polyhydric alcohol (A) is not particularly limited as long as it has a plurality of hydroxy groups in the molecule, but one having three or more hydroxy groups in the molecule is preferable.
The epoxy compound of the present invention is a compound having an epoxy group and a hydroxy group derived from a hydrolyzed epoxy group, but having three or more hydroxy groups in the molecule as the aliphatic polyhydric alcohol (A) When the aliphatic polyhydric alcohol (A) is glycidyl-etherified, when a part of the epoxy group is hydrolyzed, only a part of the epoxy group is surely hydrolyzed to hydrolyze the epoxy group in the epoxy compound. It is because the hydroxy group derived from the decomposed epoxy group can coexist.
分子内に３つ以上のヒドロキシ基を有する脂肪族多価アルコール（Ａ）としては、例えば、グリセリン、トリメチロールプロパン、トリメチロールエタン、ジグリセリン、トリグリセリン、テトラグリセリン、ポリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、ソルビタン、グルコース、ガラクトース、二糖類（ラクトース、マルトース等）、多糖類（デンプン、グリコーゲン、セルロース等）等が挙げられる。 Examples of aliphatic polyhydric alcohols (A) having three or more hydroxy groups in the molecule include glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, tetraglycerin, polyglycerin, pentaerythritol, and diglycerin. Examples include pentaerythritol, sorbitol, sorbitan, glucose, galactose, disaccharides (lactose, maltose and the like), polysaccharides (starch, glycogen, cellulose and the like) and the like.
また、上記ヒドロキシ化合物をグリシジルエーテル化してなる分子内に複数のエポキシ基を有する化合物としては、上記脂肪族多価アルコール（Ａ）をグリシジルエーテル化してなるもの以外にも、上記脂肪族多価アルコール（Ａ）をエチレンオキサイド及び／又はプロピレンオキサイドで変性した脂肪族多価アルコール（Ａ′）をグリシジルエーテル化してなるものであってもよい。ここで、上記脂肪族多価アルコール（Ａ′）は、上記脂肪族多価アルコール（Ａ）中のヒドロキシル基の全てに対して、ヒドロキシル基１つあたり１つ以上のエチレンオキサイド及び／又はプロピレンオキサイドが付加したものであっても良いし、上記脂肪族多価アルコール（Ａ）中のヒドロキシル基の一部に対して、ヒドロキシル基１つあたり１つ以上のエチレンオキサイド及び／又はプロピレンオキサイドが付加したものであっても良い。 Moreover, as a compound which has a several epoxy group in the molecule | numerator formed by glycidyl-etherifying the said hydroxy compound, the said aliphatic polyhydric alcohol besides what is formed by glycidyl-etherifying the said aliphatic polyhydric alcohol (A) It may be obtained by glycidyl etherifying (A) an aliphatic polyhydric alcohol (A ') modified with ethylene oxide and / or propylene oxide. Here, the aliphatic polyhydric alcohol (A ′) is one or more ethylene oxide and / or propylene oxide per hydroxyl group with respect to all the hydroxyl groups in the aliphatic polyhydric alcohol (A). Or one or more of ethylene oxide and / or propylene oxide is added per hydroxyl group to a part of hydroxyl groups in the aliphatic polyhydric alcohol (A). It may be something.
上記ヒドロキシ化合物をグリシジルエーテル化してなる分子内に複数のエポキシ基を有する化合物として、脂肪族多価アルコール（Ａ）をエチレンオキサイド及び／又はプロピレンオキサイドで変性した脂肪族多価アルコール（Ａ′）をグリシジルエーテル化してなるものを使用した場合は、グリシジルエーテル化した後、エポキシ基の一部を加水分解する際に、加水分解性を制御するための親水性または水溶性の調整が容易になる。また、上記脂肪族多価アルコール（Ａ′）を使用することによりエポキシ化合物の粘度を制御しやすいため取り扱い性を向上させやすい。さらに、エポキシ化合物を硬化させた際に、硬化物の物性を制御するための架橋点間距離の調整を容易に行うことができる。 Aliphatic polyhydric alcohol (A ') obtained by modifying aliphatic polyhydric alcohol (A) with ethylene oxide and / or propylene oxide as a compound having a plurality of epoxy groups in a molecule formed by glycidyl etherifying the above-mentioned hydroxy compound When using what becomes glycidyl-etherified, after glycidyl-etherified, when hydrolyzing a part of epoxy group, adjustment of the hydrophilicity or water solubility for controlling hydrolysability becomes easy. Moreover, by using the aliphatic polyhydric alcohol (A '), the viscosity of the epoxy compound can be easily controlled, and thus the handleability can be easily improved. Furthermore, when the epoxy compound is cured, it is possible to easily adjust the distance between crosslinking points to control the physical properties of the cured product.
また、上記脂肪族多価アルコール（Ａ）をエチレンオキサイドやプロピレンオキサイドで変性して脂肪族多価アルコール（Ａ′）にする方法としては、従来公知の方法を用いることができる。 Further, as a method of modifying the aliphatic polyhydric alcohol (A) with ethylene oxide or propylene oxide to obtain an aliphatic polyhydric alcohol (A '), conventionally known methods can be used.
本発明のエポキシ化合物は、上記分子内に複数のエポキシ基を有する化合物の一部のエポキシ基を加水分解してなるものである。
ここで、エポキシ基の一部を加水分解する方法としては特に限定されず、例えば、エポキシ化合物に水を加えて加熱する方法、エポキシ化合物に酢酸等の弱酸と水とを加えて加熱する方法、エポキシ化合物にアルカリ金属水酸化物やアルカリ金属炭酸塩等の塩基と水とを加えて加熱する方法等が挙げられる。
The epoxy compound of the present invention is obtained by hydrolyzing part of the epoxy group of the compound having a plurality of epoxy groups in the molecule.
Here, the method of hydrolyzing a part of the epoxy group is not particularly limited. For example, a method of adding water to an epoxy compound and heating, a method of adding a weak acid such as acetic acid and water to an epoxy compound and heating, Examples thereof include a method of adding a base such as an alkali metal hydroxide or an alkali metal carbonate and water to an epoxy compound and heating.
また、これらの方法で加水分解を行う場合、イオン交換樹脂や無機イオン交換体の存在下で反応を行ってもよい。
イオン交換樹脂や無機イオン交換体が存在する場合、低温で加水分解反応を進行させることができる。
When hydrolysis is carried out by these methods, the reaction may be carried out in the presence of an ion exchange resin or an inorganic ion exchanger.
When an ion exchange resin or an inorganic ion exchanger is present, the hydrolysis reaction can be allowed to proceed at a low temperature.
上記イオン交換樹脂を使用する場合には、例えば、市販の陽イオン交換樹脂又は陰イオン交換樹脂をそれぞれ単独で用いてもよく、また、これらの両方を同時に用いてもよい。
上記イオン交換樹脂としては特に限定されないが、例えば、スチレン−ジビニルベンゼン共重合体を母体とするスルホン酸基や四級アンモニウム基を含有する樹脂、一級から三級のアミノ基やカルボン酸基を側鎖に持つポリ（メタ）アクリル酸系の樹脂等が挙げられる。
上記無機イオン交換体としては、例えば、粘土鉱物、ゼオライト等が挙げられる。
When the above ion exchange resin is used, for example, a commercially available cation exchange resin or anion exchange resin may be used alone, or both of them may be used simultaneously.
The ion exchange resin is not particularly limited, but for example, a resin containing a sulfonic acid group or a quaternary ammonium group based on a styrene-divinylbenzene copolymer, a primary to tertiary amino group or a carboxylic acid group The resin etc. of the poly (meth) acrylic acid system which has a chain are mentioned.
As said inorganic ion exchanger, a clay mineral, a zeolite, etc. are mentioned, for example.
また、本発明のエポキシ化合物は、上述した通り、ヒドロキシ化合物をグリシジルエーテル化（エポキシ化）し、更にエポキシ基を加水分解してなるものであるが、ここでグリシジルエーテル化の反応と、エポキシ基を加水分解する反応とは同時に進行させても良い。
具体的には、例えば、ヒドロキシ化合物とエピハロヒドリンとを塩基性化合物の存在下で反応させる際に、反応混合物の水分量を２重量％以上に調整する方法が挙げられる。この方法では、塩基性化合物の添加時に水分量を調節してもよいし、塩基性化合物の添加後に水分量を調節して撹拌熟成を行ってもよい。このとき、反応混合物の水分量は、２〜１０重量％程度が好ましく、２重量％より少ないと加水分解の効率が悪くなり、１０重量％を超えるとグリシジルエーテル化率が悪くなる場合がある。
Further, as described above, the epoxy compound of the present invention is obtained by glycidyl etherifying (epoxidizing) a hydroxy compound and further hydrolyzing an epoxy group, wherein the reaction of glycidyl etherification and the epoxy group are carried out. The reaction may be carried out simultaneously with the hydrolysis reaction.
Specifically, for example, when reacting a hydroxy compound and an epihalohydrin in the presence of a basic compound, a method of adjusting the water content of the reaction mixture to 2% by weight or more can be mentioned. In this method, the water content may be adjusted at the time of addition of the basic compound, or after the addition of the basic compound, the water content may be adjusted to carry out stirring and aging. At this time, the water content of the reaction mixture is preferably about 2 to 10% by weight, and if it is less than 2% by weight, the efficiency of hydrolysis may deteriorate, and if it exceeds 10% by weight, the glycidyl etherification rate may deteriorate.
本発明のエポキシ化合物は、上述した通り、ヒドロキシ化合物をグリシジルエーテル化する工程に引き続き、エポキシ基を加水分解させる工程を経て合成される。
このとき、ヒドロキシ化合物のグリシジルエーテル化の工程において、そのグリシジル化率（グリシジルエーテル化されるヒドロキシ基の比率）は、７０％以上が好ましく、８５％以上がより好ましい。グリシジル化率が７０％未満の場合は、得られるエポキシ化合物のエポキシ基の含有量が少なくなり、硬化剤との反応において硬化不良を起こす可能性がある。また、加水分解されて生成するα−ジオールの含有量も少なくなることから、高い密着性を得ることが難しくなる場合がある。
As described above, the epoxy compound of the present invention is synthesized through the step of hydrolyzing an epoxy group subsequent to the step of glycidyl etherifying a hydroxy compound.
At this time, in the step of glycidyl etherification of a hydroxy compound, the glycidylation ratio (ratio of hydroxy group to be glycidyl etherified) is preferably 70% or more, more preferably 85% or more. When the glycidylation ratio is less than 70%, the epoxy group content of the obtained epoxy compound decreases, which may cause curing failure in the reaction with the curing agent. In addition, since the content of α-diol produced by hydrolysis is also reduced, it may be difficult to obtain high adhesion.
また、本発明のエポキシ化合物は、上記脂肪族多価アルコール（Ａ）又は上記脂肪族多価アルコール（Ａ′）をグリシジルエーテル化した際のエポキシ含量の５〜４０％に相当するエポキシ基を加水分解してなるものであることが好ましい。
なお、上記脂肪族多価アルコール（Ａ）又は上記脂肪族多価アルコール（Ａ′）をグリシジルエーテル化した際のエポキシ含量は、グリシジルエーテル化する前に脂肪族多価アルコール（Ａ）又は（Ａ′）が有していたエポキシ基と、グリシジルエーテル化により導入されたエポキシ基の両方をあわせたエポキシ基の総含量である。
加水分解したエポキシ基の割合が、上記範囲にあると、金属同士、合成樹脂同士、及び、金属と合成樹脂との各接着性に極めて優れたエポキシ化合物を提供することができるのに対し、上記割合が５％未満では、充分な接着性が発現しない場合があり、一方で、４０％を超えると、エポキシ基が不足する結果、充分な接着性が発現しなかったり、上記エポキシ化合物を硬化させた際に、硬化物のネットワークポリマーに取り込まれにくくなりブリードアウトの危険性が高まる原因となったりする場合がある。
In addition, the epoxy compound of the present invention hydrolyzes an epoxy group corresponding to 5 to 40% of the epoxy content when glycidyl-etherifying the above-mentioned aliphatic polyhydric alcohol (A) or the above-mentioned aliphatic polyhydric alcohol (A '). It is preferable that it is decomposed.
In addition, the epoxy content at the time of glycidyl-etherifying said aliphatic polyhydric alcohol (A) or said aliphatic polyhydric alcohol (A ') is aliphatic polyhydric alcohol (A) or (A) before glycidyl-etherifying. It is the total content of the epoxy group which put together the epoxy group which '' had, and the epoxy group introduce | transduced by glycidyl etherification.
When the proportion of the hydrolyzed epoxy group is in the above range, an epoxy compound extremely excellent in adhesion between metals, between synthetic resins, and between metal and synthetic resin can be provided, while the above-mentioned is compared with the above. If the proportion is less than 5%, sufficient adhesion may not be exhibited, while if it exceeds 40%, the epoxy group runs short, so that sufficient adhesion is not expressed, or the above epoxy compound is cured. At the same time, it may be difficult to be incorporated into the network polymer of the cured product, which may cause an increase in the risk of bleed out.
このような構成からなる本発明のエポキシ化合物は、後述するようにエポキシ組成物とすることにより、金属同士、合成樹脂同士、及び、金属と合成樹脂との各接着性に極めて優れた接着剤となる。
金属との接着性について、金属との優れた接着性は、金属表面に存在する水酸基等の極性基と水酸基との水素結合により達成されるものであると考えられる。本発明のエポキシ化合物には、エポキシ基を加水分解することにより、分子内に加水分解されたエポキシ基に由来するα−ジオールと呼ばれる構造を有する水酸基が存在することとなるが、このα−ジオール構造の水酸基は水酸基同士が隣接した位置に存在するため、離れた場所に存在する単独の水酸基に比べて、より強固な水素結合を形成しやすく、このような水素結合の形成が金属との優れた接着性を達成する理由と考えられる。
また、金属の場合と同様に、合成樹脂との接着においては、合成樹脂中に存在する極性を有する様々な結合や官能基、例えば、エステル結合、アミド結合、水酸基、カルボキシル基等と、α−ジオール構造の水酸基とが強固な水素結合を形成するため、合成樹脂との間で優れた接着性を確保することができると考えられる。
The epoxy compound of the present invention having such a constitution is an adhesive composition which is extremely excellent in adhesion between metals, between synthetic resins, and between metal and synthetic resin by using epoxy composition as described later. Become.
With regard to adhesion to metals, it is believed that excellent adhesion to metals is achieved by hydrogen bonding of polar groups such as hydroxyl groups present on the metal surface with hydroxyl groups. In the epoxy compound of the present invention, by hydrolyzing an epoxy group, a hydroxyl group having a structure called α-diol derived from the hydrolyzed epoxy group is present in the molecule, but this α-diol Since the hydroxyl group of the structure is present at a position where the hydroxyl groups are adjacent to each other, it is easier to form a stronger hydrogen bond than a single hydroxyl group present at a distant place, and such hydrogen bond formation is excellent with metal Is considered to be the reason for achieving good adhesion.
Further, as in the case of metal, in bonding with a synthetic resin, various polar bonds or functional groups present in the synthetic resin, for example, an ester bond, an amide bond, a hydroxyl group, a carboxyl group, etc. Since a strong hydrogen bond is formed with the hydroxyl group of the diol structure, it is considered that excellent adhesiveness with the synthetic resin can be secured.
次に、本発明のエポキシ組成物について説明する。
本発明のエポキシ組成物は、本発明のエポキシ化合物を含有することを特徴とする。
上記エポキシ組成物は、本発明のエポキシ化合物を含有していれば、必要に応じて他の成分を含有していてもよい。
上記他の成分としては、例えば、硬化剤、硬化触媒、無機充填材、シランカップリング剤、離型剤、顔料、乳化剤、難燃付与剤等が挙げられる。
Next, the epoxy composition of the present invention will be described.
The epoxy composition of the present invention is characterized by containing the epoxy compound of the present invention.
The above epoxy composition may contain other components as needed as long as it contains the epoxy compound of the present invention.
As said other component, a hardening | curing agent, a hardening catalyst, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, an emulsifier, a flame retardant imparting agent etc. are mentioned, for example.
上記硬化剤としては特に限定されず、例えば、アミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物等が挙げられる。 It does not specifically limit as said hardening | curing agent, For example, an amine compound, an acid anhydride type compound, an amide type compound, a phenol type compound etc. are mentioned.
上記アミン系化合物としては、例えば、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ペンタエチレンヘキサミン等の脂肪族ポリアミン類や、メタキシリレンジアミン、ジアミノジフェニルメタン、フェニレンジアミン等の芳香族ポリアミン類や、１、３−ビス（アミノメチル）シクロヘキサン、イソホロンジアミン、ノルボルナンジアミン等の脂環族ポリアミン類等や、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられる。 Examples of the amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, etc., metaxylylenediamine, diaminodiphenylmethane, phenylenediamine and the like. Aromatic polyamines, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophorone diamine, norbornane diamine, etc., polyamide resin synthesized from dicyandiamide, dimer of linolenic acid and ethylene diamine, etc. Can be mentioned.
上記酸無水物系化合物としては、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチル−ヘキサヒドロ無水フタル酸等が挙げられる。 Examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, Methyl-hexahydrophthalic anhydride and the like can be mentioned.
上記フェノール系化合物としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂、アミノトリアジン変性フェノール樹脂やこれらの変性物等が挙げられる。また潜在性触媒として、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体なども挙げられる。 Examples of the phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetrapheny Examples thereof include roll ethane resin, naphthol novolac resin, naphthol-phenol co-convoluted novolac resin, naphthol-cresol co-convoluted novolac resin, biphenyl modified phenolic resin, aminotriazine modified phenolic resin, and modified products thereof. Further, examples of the latent catalyst include imidazole, BF 3 -amine complex, guanidine derivative and the like.
これらの硬化剤は単独で用いてもよく、２種以上を併用してもよい。
上記硬化剤の配合量は特に制限されないが、エポキシ基１モルに対して、硬化剤の官能基が０．７〜１．５モルとなる量であることが好ましい。
硬化剤の官能基とは、アミン系硬化剤やフェノール系硬化剤であれば、活性水素のことをいい、酸無水物系硬化剤であれば、酸無水物基のことをいう。
These curing agents may be used alone or in combination of two or more.
Although the compounding quantity in particular of the said hardening agent is not restrict | limited, It is preferable that it is the quantity used as 0.7-1.5 mol of functional groups of a hardening agent with respect to 1 mol of epoxy groups.
The functional group of the curing agent means active hydrogen if it is an amine-based curing agent or a phenol-based curing agent, and it means an acid anhydride group if it is an acid anhydride-based curing agent.
上記硬化触媒としては、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。
上記硬化触媒の添加量は特に限定されないが、通常、エポキシ化合物に対して、０．１〜１０重量％程度である。
Examples of the curing catalyst include phosphorus compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, amine complexes and the like.
Although the addition amount of the said curing catalyst is not specifically limited, Usually, it is about 0.1 to 10 weight% with respect to an epoxy compound.
上記無機充填材としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。
上記無機充填材の配合量は特に制限されないが、通常、エポキシ組成物中５〜９０重量％程度である。
好ましい無機充填材の配合量は、５０〜９０重量％である。通常、エポキシ組成物を含む接着剤において無機充填材の配合量が多くなると接着力が低下する傾向にあるのに対し、本発明のエポキシ化合物を含む接着剤では、無機充填材の配合量が上記のように多くなっても接着力の低下が抑えられるからである。
Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride and aluminum hydroxide.
Although the compounding quantity in particular of the said inorganic filler is not restrict | limited, Usually, it is about 5-90 weight% in an epoxy composition.
The preferred compounding amount of the inorganic filler is 50 to 90% by weight. In general, when the compounding amount of the inorganic filler in the adhesive containing the epoxy composition increases, the adhesive force tends to decrease, but in the adhesive containing the epoxy compound of the present invention, the compounding amount of the inorganic filler is the above This is because the decrease in adhesion can be suppressed even if the
上記難燃付与剤としては、例えば、デカブロモジフェニルエーテル、テトラブロモビスフェノールＡ等のハロゲン化合物、赤リンや各種燐酸エステル化合物等の燐原子含有化合物、メラミン或いはその誘導体等の窒素原子含有化合物、水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウム等の無機系難燃化合物が挙げられる。
上記難燃付与剤の配合量は特に制限されないが、通常、エポキシ組成物中に、１〜２０重量％程度含まれるように配合する。
Examples of the flame retardants include halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A, phosphorus-containing compounds such as red phosphorus and various phosphoric acid ester compounds, nitrogen atom-containing compounds such as melamine and derivatives thereof, and hydroxylation Inorganic flame retardant compounds such as aluminum, magnesium hydroxide, zinc borate and calcium borate can be mentioned.
Although the compounding quantity of the said flame retardant imparting agent is not specifically limited, Usually, it mix | blends so that about 1 to 20 weight% may be contained in an epoxy composition.
上記シランカップリング剤としては、例えば、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン等の（メタ）アクリロキシシラン類；３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン類；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、ジメチルビニルメトキシシラン、ビニルトリクロロシラン、ジメチルビニルクロロシラン等のビニルシラン類；Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン等のアミノシラン類などが挙げられる。 Examples of the silane coupling agent include (meth) acryloxysilanes such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane; 3-glycidoxypropyltri Epoxysilanes such as methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc .; vinyltrimethoxysilane, vinyl Vinylsilanes such as triethoxysilane, vinyltris (β-methoxyethoxy) silane, dimethylvinylmethoxysilane, vinyltrichlorosilane and dimethylvinylchlorosilane; N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- Mino trimethoxysilane, N-2- (aminoethyl) -3 and aminopropyl aminosilanes such as methyl dimethoxy silane.
上記離型剤としては、例えば、カルナバワックスなどの天然系ワックス、ポリエチレンワックスなどのポリオレフィン系ワックス、シリコーンオイルなどのシリコーン化合物、モンタン酸アミドなどのアミド系ワックス、モンタン酸エステルなどのエステル系ワックス、ステアリン酸などの高級脂肪酸、ステアリン酸亜鉛などの高級脂肪酸の金属塩類等が挙げられる。 Examples of the mold release agent include natural waxes such as carnauba wax, polyolefin waxes such as polyethylene wax, silicone compounds such as silicone oil, amide waxes such as montanic acid amide, ester waxes such as montanic acid ester, Examples thereof include higher fatty acids such as stearic acid, and metal salts of higher fatty acids such as zinc stearate.
上記顔料としては、例えば、カーボンブラック、ベンガラ、酸化鉄、亜鉛粉末、二酸化チタン、フタロシアニンブルー、フタロシアニングリーン、キナクリドン系顔料、アゾ系顔料、イソインドリノン系顔料、各種焼成顔料等の着色顔料、シリカ、タルク、硫酸バリウム、炭酸カルシウム、ガラスフレーク等の体質顔料等が挙げられる。 Examples of the pigment include carbon black, red iron oxide, iron oxide, zinc powder, titanium dioxide, phthalocyanine blue, phthalocyanine green, quinacridone pigments, azo pigments, isoindolinone pigments, colored pigments such as various calcined pigments, silica And extender pigments such as talc, barium sulfate, calcium carbonate and glass flakes.
上記乳化剤としては、例えば、アニオン系、カチオン系、ノニオン系の公知の乳化剤を使用することが出来る。 As the emulsifier, for example, known anionic, cationic or nonionic emulsifiers can be used.
このような構成からなるエポキシ組成物は、例えば、接着剤として好適に使用することができ、金属同士の接着剤、合成樹脂同士の接着剤、及び、金属と合成樹脂との接着剤として特に適している。
上記エポキシ組成物を含む接着剤もまた本発明の１つである。
The epoxy composition having such a constitution can be suitably used as, for example, an adhesive, and is particularly suitable as an adhesive between metals, an adhesive between synthetic resins, and an adhesive between metals and synthetic resins. ing.
An adhesive comprising the above epoxy composition is also one of the present invention.
以下に、実施例を挙げて本発明を説明するが、本発明はこれらの実施例のみに限定されるわけではない。なお、下記表１には、下記参考合成例及び合成例の内容をまとめて示した。 EXAMPLES The present invention will be described by way of examples, but the present invention is not limited to these examples. Table 1 below summarizes the contents of the following Reference Synthesis Examples and Synthesis Examples.
（エポキシ化合物の分析）
加水分解前後のエポキシ化合物のエポキシ含量は、ＪＩＳ Ｋ−７２３６に準じて測定した。
本発明のエポキシ化合物におけるエポキシ基の加水分解量は、エポキシ基の加水分解により生成するα−ジオール（１，２−グリコール）量に等しいことから、α−ジオールの含有量を、過ヨウ素酸を用いた酸化法により測定した（過ヨウ素酸を用いた方法については、ＢＵＮＳＥＫＩ ＫＡＧＡＫＵ Ｖｏｌ．５７，Ｎｏ．６， ｐｐ．４９９−５０３（２００８）等を参照のこと）。
(Analysis of epoxy compounds)
The epoxy content of the epoxy compound before and after hydrolysis was measured according to JIS K-7236.
Since the hydrolysis amount of the epoxy group in the epoxy compound of the present invention is equal to the amount of α-diol (1,2-glycol) generated by hydrolysis of the epoxy group, the content of α-diol is It was measured by the oxidation method used (for the method using periodic acid, see BUNSEKI KAGAKU Vol. 57, No. 6, pp. 499-503 (2008), etc.).
（参考合成例１）
撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ソルビトールのヒドロキシ基にエチレンオキサイド（ＥＯ）を付加させた多価アルコール（水酸基価＝７８０ｍｇＫＯＨ／ｇ）１８０ｇに、エピクロルヒドリンを７００ｇ加え、さらにテトラメチルアンモニウムクロライドを５．４ｇ加え、減圧下で液温度を５５〜６５℃に保ち、あわせて水を除去しながら、４９％液体苛性ソーダ２００ｇを４時間かけて滴下して、引き続き１時間の熟成を行った。
得られた反応液に対して、生成した塩濃度が１０％水溶液となるように軟水を加えて撹拌溶解し、エピクロルヒドリン層を分離抽出して、生成塩を除去したのち、軟水で有機層を洗い、エバポレータにより１００℃で減圧濃縮を行って有機層からエピクロルヒドリンを除去してエポキシ化合物を得た。
このエポキシ化合物のエポキシ含量は、１３５ｇ／ｅｑであった。また、このエポキシ化合物のα−ジオール含量は、２０，０００ｇ／ｅｑであった。α−ジオールは、エポキシ基の加水分解により生成することから、エポキシ基の約０．７％が加水分解している事が判明した。
(Reference synthesis example 1)
In a 1000 ml reactor equipped with a stirrer, condenser and thermometer, add 700 g of epichlorohydrin to 180 g of polyhydric alcohol (hydroxyl number = 780 mg KOH / g) prepared by adding ethylene oxide (EO) to the hydroxyl group of sorbitol. Add 5.4 g of tetramethylammonium chloride, keep the solution temperature at 55 to 65 ° C under reduced pressure, add 200 g of 49% liquid caustic soda over 4 hours while removing water, and then continue aging for 1 hour Did.
Soft water is added to the resulting reaction solution so that the concentration of the generated salt is a 10% aqueous solution, stirred and dissolved, the epichlorohydrin layer is separated and extracted, the formed salt is removed, and the organic layer is washed with soft water The solution was concentrated under reduced pressure at 100 ° C. by an evaporator to remove epichlorohydrin from the organic layer to obtain an epoxy compound.
The epoxy content of this epoxy compound was 135 g / eq. Moreover, the alpha-diol content of this epoxy compound was 20,000 g / eq. The α-diol was formed by hydrolysis of the epoxy group, and it was found that about 0.7% of the epoxy group was hydrolyzed.
（合成例１）
撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ソルビトールのヒドロキシ基にエチレンオキサイド（ＥＯ）を付加させた多価アルコール（水酸基価＝７８０ｍｇＫＯＨ／ｇ）１８０ｇに、エピクロルヒドリンを７００ｇ加え、さらにテトラメチルアンモニウムクロライドを５．４ｇ加え、減圧下で液温度を５５〜６５℃に保ち、あわせて水を除去しながら、４９％液体苛性ソーダ１６０ｇを４時間かけて滴下して、引き続き、反応液の水分含量が５重量％となるように調製した後、１時間の熟成を行った。
得られた反応液に対して、生成した塩濃度が１０％水溶液となるように軟水を加えて撹拌溶解し、エピクロルヒドリン層を分離抽出して、生成塩を除去したのち、軟水で有機層を洗い、エバポレータにより１００℃で減圧濃縮を行って有機層からエピクロルヒドリンを除去してエポキシ化合物を得た。
このエポキシ化合物のエポキシ含量は１７０ｇ／ｅｑ、α−ジオール含量は、２，０００ｇ／ｅｑであった。この結果より、エポキシ基の約９％が加水分解している事が判明した。
Synthesis Example 1
In a 1000 ml reactor equipped with a stirrer, condenser and thermometer, add 700 g of epichlorohydrin to 180 g of polyhydric alcohol (hydroxyl number = 780 mg KOH / g) prepared by adding ethylene oxide (EO) to the hydroxyl group of sorbitol. After adding 5.4 g of tetramethyl ammonium chloride, maintaining the solution temperature at 55 to 65 ° C. under reduced pressure and simultaneously removing water, 160 g of 49% liquid caustic soda is added dropwise over 4 hours, and After adjusting the water content to 5% by weight, aging was performed for 1 hour.
Soft water is added to the resulting reaction solution so that the concentration of the generated salt is a 10% aqueous solution, stirred and dissolved, the epichlorohydrin layer is separated and extracted, the formed salt is removed, and the organic layer is washed with soft water The solution was concentrated under reduced pressure at 100 ° C. by an evaporator to remove epichlorohydrin from the organic layer to obtain an epoxy compound.
The epoxy content of this epoxy compound was 170 g / eq, and the α-diol content was 2,000 g / eq. From this result, it was found that about 9% of the epoxy groups were hydrolyzed.
（合成例２）
撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ソルビトールのヒドロキシ基にエチレンオキサイド（ＥＯ）を付加させた多価アルコール（水酸基価＝７８０ｍｇＫＯＨ／ｇ）１８０ｇに、エピクロルヒドリンを７００ｇ加え、さらにテトラメチルアンモニウムクロライドを５．４ｇ加え、減圧下で液温度を５５〜６５℃に保ち、あわせて水を除去しながら、４９％液体苛性ソーダ２００ｇを４時間かけて滴下して、引き続き１時間の熟成を行った。
得られた反応液に対して、生成した塩濃度が１０％水溶液となるように軟水を加えて撹拌溶解し、エピクロルヒドリン層を分離抽出して、生成塩を除去したのち、軟水で有機層を洗い、エバポレータにより１００℃で減圧濃縮を行って有機層からエピクロルヒドリンを除去して、エポキシ化合物を得た。
このエポキシ化合物のエポキシ含量は、１３５ｇ／ｅｑ、α−ジオール含量は、２０，０００ｇ／ｅｑであった。
引き続き、このエポキシ化合物１００重量部に対してイオン交換水を５０重量部加えて９０℃で加熱撹拌して、エポキシ基の一部を加水分解させた後に、あらためてエバポレータにより１００℃で減圧濃縮を行って、エポキシ基の一部が加水分解したエポキシ化合物を得た。このエポキシ化合物のエポキシ含量は１６６ｇ／ｅｑ、α−ジオール含量は７１５ｇ／ｅｑであった。この結果より、エポキシ基の約１９％が加水分解されていることが判明した。
(Composition example 2)
In a 1000 ml reactor equipped with a stirrer, condenser and thermometer, add 700 g of epichlorohydrin to 180 g of polyhydric alcohol (hydroxyl number = 780 mg KOH / g) prepared by adding ethylene oxide (EO) to the hydroxyl group of sorbitol. Add 5.4 g of tetramethylammonium chloride, keep the solution temperature at 55 to 65 ° C under reduced pressure, add 200 g of 49% liquid caustic soda over 4 hours while removing water, and then continue aging for 1 hour Did.
Soft water is added to the resulting reaction solution so that the concentration of the generated salt is a 10% aqueous solution, stirred and dissolved, the epichlorohydrin layer is separated and extracted, the formed salt is removed, and the organic layer is washed with soft water The solution was concentrated under reduced pressure at 100 ° C. by an evaporator to remove epichlorohydrin from the organic layer to obtain an epoxy compound.
The epoxy content of this epoxy compound was 135 g / eq, and the α-diol content was 20,000 g / eq.
Subsequently, 50 parts by weight of ion-exchanged water is added to 100 parts by weight of the epoxy compound, and the mixture is heated and stirred at 90 ° C. to hydrolyze a part of the epoxy groups, and then concentrated again under reduced pressure at 100 ° C. by an evaporator. Thus, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained. The epoxy content of this epoxy compound was 166 g / eq, and the α-diol content was 715 g / eq. From this result, it was found that about 19% of the epoxy groups were hydrolyzed.
（合成例３）
ソルビトールのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝７１４ｍｇＫＯＨ／ｇ）を用いて、参考合成例１と同様にしてエポキシ化合物を合成した後、引き続き、このエポキシ化合物１００重量部に対してイオン交換水を４０重量部加えて９５℃で加熱撹拌して、エポキシ基の一部を加水分解させた後に、あらためてエバポレータにより１００℃で減圧濃縮を行って、エポキシ基の一部が加水分解したエポキシ化合物を得た。
(Composition example 3)
An epoxy compound was synthesized in the same manner as in Reference Synthesis Example 1 using a polyhydric alcohol (hydroxyl value = 714 mg KOH / g) prepared by adding ethylene oxide to the hydroxyl group of sorbitol, and subsequently, 100 parts by weight of this epoxy compound To 40 parts by weight of ion-exchanged water is added, and the mixture is heated and stirred at 95 ° C. to hydrolyze a part of the epoxy group, and then concentrated again under reduced pressure at 100 ° C. by an evaporator to hydrolyze part of the epoxy group The decomposed epoxy compound was obtained.
（合成例４）
ソルビトールのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝１０１８ｍｇＫＯＨ／ｇ）を用いて、参考合成例１と同様にしてエポキシ化合物を合成した後、引き続き、このエポキシ化合物１００重量部に対してイオン交換水を４０重量部加えて９５℃で加熱撹拌して、エポキシ基の一部を加水分解させた後に、あらためてエバポレータにより１００℃で減圧濃縮を行って、エポキシ基の一部が加水分解したエポキシ化合物を得た。
(Composition example 4)
An epoxy compound was synthesized in the same manner as in Reference Synthesis Example 1 using a polyhydric alcohol (hydroxyl value = 1018 mg KOH / g) prepared by adding ethylene oxide to the hydroxyl group of sorbitol, and subsequently, 100 parts by weight of this epoxy compound To 40 parts by weight of ion-exchanged water is added, and the mixture is heated and stirred at 95 ° C. to hydrolyze a part of the epoxy group, and then concentrated again under reduced pressure at 100 ° C. by an evaporator to hydrolyze part of the epoxy group The decomposed epoxy compound was obtained.
（合成例５）
多価アルコールとして、撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ソルビトールのヒドロキシ基にプロピレンオキサイド（ＰＯ）を付加させた多価アルコール（水酸基価＝４８９ｍｇＫＯＨ／ｇ）１８０ｇを用いた以外は、合成例２と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
(Composition example 5)
As a polyhydric alcohol, 180 g of polyhydric alcohol (hydroxyl number = 489 mg KOH / g) prepared by adding propylene oxide (PO) to hydroxyl group of sorbitol was used in a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer. An epoxy compound was obtained in the same manner as in Synthesis Example 2 except that a part of the epoxy group was hydrolyzed.
（合成例６）
多価アルコールとして、撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ペンタエリスリトールのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝６９９ｍｇＫＯＨ／ｇ）１８０ｇを用いた以外は、合成例２と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 6
As polyvalent alcohol, polyvalent alcohol (hydroxyl value = 699 mg KOH / g) obtained by adding ethylene oxide to hydroxy group of pentaerythritol in a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer is used except for 180 g In the same manner as in Synthesis Example 2, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained.
（合成例７）
多価アルコールとして、撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、トリメチロールプロパンのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝６１６ｍｇＫＯＨ／ｇ）１８０ｇを用いた以外は、合成例２と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 7
Except that, in a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer, 180 g of a polyhydric alcohol in which ethylene oxide is added to the hydroxy group of trimethylolpropane (hydroxyl value = 616 mg KOH / g) is used as a polyhydric alcohol. In the same manner as in Synthesis Example 2, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained.
（合成例８）
多価アルコールとして、撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、グリセロールのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝７２０ｍｇＫＯＨ／ｇ）１８０ｇを用いた以外は、合成例２と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 8
As a polyhydric alcohol, in a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer, 180 g of polyhydric alcohol (hydroxyl value = 720 mg KOH / g) obtained by adding ethylene oxide to hydroxyl group of glycerol was used, In the same manner as in Synthesis Example 2, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained.
（合成例９）
エポキシ化合物を加水分解する方法として、２５重量部のイオン交換樹脂（ダウ・ケミカル社製、アンバーリスト１５ＪＷＥＴ）の存在下、エポキシ化合物１００重量部に対してイオン交換水を５０重量部加えて４０℃で加熱撹拌する方法を採用した以外は、合成例３と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 9
As a method of hydrolyzing an epoxy compound, 50 parts by weight of ion exchanged water is added to 100 parts by weight of an epoxy compound in the presence of 25 parts by weight of ion exchange resin (Amberlyst 15JWET, manufactured by Dow Chemical Co.), and 40 ° C. An epoxy compound in which a part of the epoxy group was hydrolyzed was obtained in the same manner as in Synthesis Example 3 except that the method of heating and stirring was adopted.
（合成例１０）
エポキシ化合物を加水分解する方法として、２５重量部のイオン交換樹脂（ダウ・ケミカル社製、アンバーリスト１５ＪＷＥＴ）の存在下、エポキシ化合物１００重量部に対してイオン交換水を５０重量部加えて４０℃で加熱撹拌する方法を採用した以外は、合成例５と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 10
As a method of hydrolyzing an epoxy compound, 50 parts by weight of ion exchanged water is added to 100 parts by weight of an epoxy compound in the presence of 25 parts by weight of ion exchange resin (Amberlyst 15JWET, manufactured by Dow Chemical Co.), and 40 ° C. An epoxy compound in which a part of the epoxy group was hydrolyzed was obtained in the same manner as in Synthesis Example 5 except that the method of heating and stirring was adopted.
（合成例１１）
エポキシ化合物を加水分解する方法として、エポキシ化合物１００重量部に対して、酢酸を２重量部、イオン交換水を５０重量部加えて９０℃で加熱撹拌する方法を採用した以外は、合成例３と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 11
As a method of hydrolyzing an epoxy compound, 2 parts by weight of acetic acid and 50 parts by weight of ion exchanged water are added to 100 parts by weight of an epoxy compound, and a method of heating and stirring at 90 ° C. is adopted. Similarly, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained.
（合成例１２）
多価アルコールとして、撹拌機と冷却管と温度計を備える１０００ｍｌの反応器に、ソルビトールのヒドロキシ基にエチレンオキサイドを付加させた多価アルコール（水酸基価＝３１７ｍｇＫＯＨ／ｇ）１８０ｇを用いた以外は、合成例２と同様にしてエポキシ基の一部が加水分解したエポキシ化合物を得た。
Synthesis Example 12
As a polyhydric alcohol, a polyhydric alcohol (hydroxyl value = 317 mg KOH / g) obtained by adding ethylene oxide to the hydroxyl group of sorbitol (hydroxyl value = 317 mg KOH / g) was used in a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer. In the same manner as in Synthesis Example 2, an epoxy compound in which a part of the epoxy group was hydrolyzed was obtained.
（合成例１３）
エポキシ含量が１６９（ｇ／ｅｑ）であるデナコールＥＸ−５１２（ナガセケムテックス社製）２００ｇを、温度計、撹拌機および冷却管を備えたフラスコに加え、引き続き、イオン交換水を８０ｇ加えて溶解し、温度を９５℃に保ちながら、エポキシ含量の内、１９％を加水分解し、引き続き減圧脱水を行って、エポキシ基の一部が加水分解されたエポキシ基を持つエポキシ化合物を得た。
Synthesis Example 13
200 g of Denacol EX-512 (manufactured by Nagase ChemteX Corp.) having an epoxy content of 169 (g / eq) is added to a flask equipped with a thermometer, a stirrer and a condenser, and then 80 g of ion exchanged water is added for dissolution Then, 19% of the epoxy content was hydrolyzed while maintaining the temperature at 95 ° C., and then dehydration was performed under reduced pressure to obtain an epoxy compound having an epoxy group in which a part of the epoxy group was hydrolyzed.
（合成例１４）
エポキシ含量が１４３（ｇ／ｅｑ）であるデナコールＥＸ−３１４（ナガセケムテックス製社）４５０ｇを、温度計、撹拌機および冷却管を備えたフラスコに加え、引き続き、イオン交換水を２２５ｇ加えて溶解し、さらに酢酸をエポキシ化合物１００重量部に対して、２重量部加えて、温度を９０℃に保ちながら、エポキシ含量の内、２９％を加水分解し、引き続き減圧脱水を行って、エポキシ基の一部が加水分解されたエポキシ基を持つエポキシ化合物を得た。
Synthesis Example 14
450 g of Denacol EX-314 (manufactured by Nagase ChemteX Corp.) having an epoxy content of 143 (g / eq) is added to a flask equipped with a thermometer, a stirrer and a condenser, and subsequently 225 g of ion exchanged water is added for dissolution And add 2 parts by weight of acetic acid to 100 parts by weight of the epoxy compound to hydrolyze 29% of the epoxy content while maintaining the temperature at 90 ° C., followed by vacuum dehydration to obtain epoxy group An epoxy compound having a partially hydrolyzed epoxy group was obtained.
（実施例１）
合成例１で得たエポキシ基の一部が加水分解されたエポキシ化合物に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
Example 1
To the epoxy compound in which a part of the epoxy group obtained in Synthesis Example 1 was hydrolyzed, 0.9 eq of Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent was cured. An epoxy composition (adhesive) was prepared by mixing 1 phr of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a catalyst.
（実施例２）
合成例３で得たエポキシ基の一部が加水分解されたエポキシ化合物に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
(Example 2)
To the epoxy compound in which a part of the epoxy group obtained in Synthesis Example 3 was hydrolyzed, 0.9 eq of Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent was cured. An epoxy composition (adhesive) was prepared by mixing 1 phr of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a catalyst.
（実施例３）
合成例２で得たエポキシ基の一部が加水分解されたエポキシ化合物に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
(Example 3)
To the epoxy compound in which a part of the epoxy group obtained in Synthesis Example 2 was hydrolyzed, 0.9 eq of Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent was cured. An epoxy composition (adhesive) was prepared by mixing 1 phr of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a catalyst.
（実施例４）
合成例４で得たエポキシ化合物に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
(Example 4)
To the epoxy compound obtained in Synthesis Example 4, 0.9 eq of Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent, and 2E4MZ (2-ethyl-4-2) as a curing catalyst An epoxy composition (adhesive) was prepared by mixing 1 phr of methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
（実施例５）
参考合成例１で得たエポキシ化合物に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
(Example 5)
To the epoxy compound obtained in Reference Synthesis Example 1, 0.9 eq of Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent, and 2E4MZ (2-ethyl-4) as a curing catalyst -An epoxy composition (adhesive) was prepared by mixing 1 phr of -Methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
（比較例１）
市販のエポキシ化合物であるＡＥＲ２６０（エポキシ含量＝１９０ｇ／ｅｑ、旭化成イーマテリアルズ社製）に、硬化剤としてＭｅ−ＨＨＰＡ（メチル−ヘキサヒドロ無水フタル酸、日立化成工業社製、ＨＮ−５５００）を０．９ｅｑ、硬化触媒として２Ｅ４ＭＺ（２−エチル−４−メチルイミダゾール、四国化成工業社製）を１ｐｈｒ混合し、エポキシ組成物（接着剤）を調製した。
(Comparative example 1)
Commercially available epoxy compound AER 260 (epoxy content = 190 g / eq, manufactured by Asahi Kasei E-Materials Co., Ltd.) and Me-HHPA (methyl-hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., HN-5500) as a curing agent An epoxy composition (adhesive) was prepared by mixing 9 eq. And 1 phr of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing catalyst.
（接着性の評価：金属同士の接着性）
実施例１〜５及び比較例１で調製したエポキシ組成物について、ＪＩＳ Ｋ６８５０に準拠したせん断接着強度を実施し、その接着力を評価した。結果を表２に示した。
ここで、測定装置としては、東洋精機製作所社製、ＳＴＲＯＧＲＡＰＨ−Ｗ２を使用した。
また、エポキシ組成物の硬化条件は、１２０℃で２時間加熱後、つづけて昇温して１６０℃で４時間加熱することとした。
更に、被着材としては、ＳＰＣＣ−ＳＢで♯７００研磨処理した鋼板（鉄板）、及び、Ａ１０５０で♯７００研磨処理したアルミ板の２種類を使用した。
(Evaluation of adhesion: adhesion between metals)
With respect to the epoxy compositions prepared in Examples 1 to 5 and Comparative Example 1, shear adhesive strength in accordance with JIS K 6850 was carried out, and the adhesive strength was evaluated. The results are shown in Table 2.
Here, as a measuring device, STROGRAPH-W2 manufactured by Toyo Seiki Seisaku-sho, Ltd. was used.
Moreover, as for the curing conditions of the epoxy composition, after heating at 120 ° C. for 2 hours, it was continuously heated and heated at 160 ° C. for 4 hours.
Further, as the adherend, two types of steel plate (iron plate) polished by # 700 with SPCC-SB and aluminum plate polished with # 1050 by # 1050 were used.
（接着性の評価：合成樹脂同士の接着性）
実施例１〜５及び比較例１で調製したエポキシ組成物を、アプリケーターを用いてポリエステルフィルム（東レ株式会社製、ルミラーＴ６０、厚さ１２５μｍ）に２０μｍの厚みで塗布し、未塗布のポリエステルフィルムを重ねゴムローラーを用いて貼り合わせ、１００℃で５時間加熱硬化させ、得られたフィルム積層体を２５ｍｍ幅の短冊状に切り出し、ＪＩＳ Ｋ６８５４−３に準拠し、引っ張り速度５０ｍｍ／分ではく離接着強さ（Ｔ型はく離）試験により評価した。評価結果（はく離接着強さの平均値）を表３に示す。
ここで、測定装置としては、東洋精機製作所社製、ＳＴＲＯＧＲＡＰＨ−Ｗ２を使用した。
(Evaluation of adhesion: adhesion between synthetic resins)
The epoxy composition prepared in Examples 1 to 5 and Comparative Example 1 is applied to a polyester film (Lumirror T60 manufactured by Toray Industries, Inc., thickness: 125 μm) using an applicator at a thickness of 20 μm, and an uncoated polyester film is obtained. The resulting film laminate is cut into 25 mm wide strips and bonded at a temperature of 50 mm / minute according to JIS K 6854-3. It was evaluated by a test (T-type peeling). Evaluation results (average peel adhesion strength) are shown in Table 3.
Here, as a measuring device, STROGRAPH-W2 manufactured by Toyo Seiki Seisaku-sho, Ltd. was used.
（接着性の評価：金属と合成樹脂との接着性）
実施例１〜５及び比較例１で調製したエポキシ組成物を、アプリケーターを用いてポリエステルフィルム（東レ株式会社製、ルミラーＴ６０、厚さ１２５μｍ）に２０μｍの厚みで塗布し、未塗布のＡ１０５０で♯７００研磨処理したアルミ板を重ねゴムローラーを用いて貼り合わせ、１００℃で５時間加熱硬化させ、得られたフィルム積層体を２５ｍｍ幅の短冊状に切り出し、ＪＩＳ Ｋ６８５４−３に準拠し、引っ張り速度５０ｍｍ／分ではく離接着強さ（Ｔ型はく離）試験により評価した。評価結果（はく離接着強さの平均値）を表３に示す。
ここで、測定装置としては、東洋精機製作所社製、ＳＴＲＯＧＲＡＰＨ−Ｗ２を使用した。
(Evaluation of adhesion: adhesion between metal and synthetic resin)
The epoxy composition prepared in Examples 1 to 5 and Comparative Example 1 is applied to a polyester film (Lumirror T60 manufactured by Toray Industries, Inc., thickness L 125 μm) using an applicator at a thickness of 20 μm, and uncoated A1050 # A 700-polished aluminum plate is stacked and bonded using a rubber roller, heat cured at 100 ° C for 5 hours, the obtained film laminate is cut into 25 mm wide strips, and the tensile speed is in accordance with JIS K6854-3. It was evaluated by a peel adhesion strength (T-type peel) test at 50 mm / min. Evaluation results (average peel adhesion strength) are shown in Table 3.
Here, as a measuring device, STROGRAPH-W2 manufactured by Toyo Seiki Seisaku-sho, Ltd. was used.
実施例及び比較例の結果より、本発明のエポキシ化合物を含むエポキシ組成物を金属や合成樹脂といった材料の接着剤として使用することにより、優れた接着性を発揮することが明らかとなった。 From the results of Examples and Comparative Examples, it became clear that excellent adhesiveness is exhibited by using the epoxy composition containing the epoxy compound of the present invention as an adhesive for materials such as metals and synthetic resins.
本発明のエポキシ化合物は、その利用分野は限定されないものの、例えば、金属や合成樹脂との接着性に優れた接着剤として極めて好適に使用することができる。 The epoxy compound of the present invention can be extremely suitably used as an adhesive having excellent adhesion to, for example, metals and synthetic resins, although the field of use is not limited.
Claims (4)
前記分子内に複数のエポキシ基を有する化合物は、脂肪族多価アルコール（Ａ）をエチレンオキサイド及び／又はプロピレンオキサイドで変性した脂肪族多価アルコール（Ａ’）をグリシジルエーテル化してなるものであるエポキシ化合物。 An epoxy compound characterized in that , in a compound having a plurality of epoxy groups in a molecule formed by glycidyl etherifying a hydroxy compound, the epoxy group corresponding to 5 to 40% of the epoxy content is hydrolyzed,
The compound having a plurality of epoxy groups in the molecule is obtained by glycidyl etherifying an aliphatic polyhydric alcohol (A ') obtained by modifying an aliphatic polyhydric alcohol (A) with ethylene oxide and / or propylene oxide. Epoxy compound.
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| BE756055A (en) * | 1969-09-12 | 1971-03-11 | Procter & Gamble | SOFT EPOXIDIC RESINS |
| JPS5626961A (en) * | 1979-07-06 | 1981-03-16 | Toyo Seikan Kaisha Ltd | Metal can paint having excellent adhesiveness with time |
| BR8108885A (en) * | 1980-11-26 | 1982-10-26 | Dow Chemical Co | PROCESS TO PREPARE HIGH MOLECULAR WEIGHT EPOXY RESINS CONTAINING HYDROLIZED GLYCYDILE GROUPS |
| WO1984000767A1 (en) * | 1982-08-16 | 1984-03-01 | Dow Chemical Co | Coating compositions containing a hydrolyzed epoxy novolac resin |
| JPH04270721A (en) * | 1991-02-26 | 1992-09-28 | Yuka Shell Epoxy Kk | Production of highly reactive high-molecular weight epoxy resin |
| USH1439H (en) * | 1993-10-18 | 1995-05-02 | The Dow Chemical Company | Method to increase the level of α-glycol in liquid epoxy resin |
| JPH08100079A (en) * | 1994-09-29 | 1996-04-16 | Sanyo Chem Ind Ltd | Crosslinking agent |
| KR20110133586A (en) * | 2009-03-04 | 2011-12-13 | 다우 글로벌 테크놀로지스 엘엘씨 | Thermosettable composition containing a glycidylether based on trimethyolpropane octadecaethoxilate |
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