JP7351258B2 - Crosslinking agent for hydrolyzable organosilane compounds and room temperature curable organopolysiloxane compositions - Google Patents
Crosslinking agent for hydrolyzable organosilane compounds and room temperature curable organopolysiloxane compositions Download PDFInfo
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- JP7351258B2 JP7351258B2 JP2020098066A JP2020098066A JP7351258B2 JP 7351258 B2 JP7351258 B2 JP 7351258B2 JP 2020098066 A JP2020098066 A JP 2020098066A JP 2020098066 A JP2020098066 A JP 2020098066A JP 7351258 B2 JP7351258 B2 JP 7351258B2
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- Prior art keywords
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- hydrolyzable organosilane
- organosilane compound
- compound
- crosslinking agent
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- 239000000203 mixture Substances 0.000 title claims description 60
- -1 organosilane compounds Chemical class 0.000 title claims description 55
- 239000003431 cross linking reagent Substances 0.000 title claims description 27
- 229920001296 polysiloxane Polymers 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000001282 organosilanes Chemical class 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 description 11
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000005046 Chlorosilane Substances 0.000 description 8
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 235000013355 food flavoring agent Nutrition 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- WOFAGNLBCJWEOE-UHFFFAOYSA-N Benzyl acetoacetate Chemical compound CC(=O)CC(=O)OCC1=CC=CC=C1 WOFAGNLBCJWEOE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- AOESAXAWXYJFNC-UHFFFAOYSA-N bis(prop-2-enyl) propanedioate Chemical compound C=CCOC(=O)CC(=O)OCC=C AOESAXAWXYJFNC-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- RYFCSKVXWRJEOB-UHFFFAOYSA-N dibenzyl propanedioate Chemical compound C=1C=CC=CC=1COC(=O)CC(=O)OCC1=CC=CC=C1 RYFCSKVXWRJEOB-UHFFFAOYSA-N 0.000 description 2
- MOJJCFBDUWMVJK-UHFFFAOYSA-N dipentyl propanedioate Chemical compound CCCCCOC(=O)CC(=O)OCCCCC MOJJCFBDUWMVJK-UHFFFAOYSA-N 0.000 description 2
- HCWOVPZEAFLXPL-UHFFFAOYSA-N diphenyl propanedioate Chemical compound C=1C=CC=CC=1OC(=O)CC(=O)OC1=CC=CC=C1 HCWOVPZEAFLXPL-UHFFFAOYSA-N 0.000 description 2
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- PFENPVAFZTUOOM-UHFFFAOYSA-N phenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC1=CC=CC=C1 PFENPVAFZTUOOM-UHFFFAOYSA-N 0.000 description 2
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 description 2
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002923 oximes Chemical group 0.000 description 1
- 125000000109 phenylethoxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、新規な加水分解性オルガノシラン化合物に関するものであり、特に加水分解によって、脱離基としてアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を放出する加水分解性オルガノシラン化合物及び室温硬化性オルガノポリシロキサン組成物の架橋剤に関する。
The present invention relates to a novel hydrolyzable organosilane compound, and particularly to a hydrolyzable organosilane compound that releases a β-ketoester compound such as acetoacetate or malonate as a leaving group upon hydrolysis, and The present invention relates to a crosslinking agent for curable organopolysiloxane compositions .
従来から、縮合硬化型の室温硬化性オルガノポリシロキサン組成物については、主として、ベースポリマーである分子鎖両末端がシラノール基（ケイ素原子に結合したヒドロキシ基）で封鎖されたオルガノポリシロキサンに対して架橋剤として加水分解性基を有するオルガノシラン化合物を用いて分子鎖末端のシラノール基を加水分解性シリル基で封鎖し、密閉容器に充填した一液タイプの製品と、ベースポリマーと加水分解性基を有する架橋剤とを別々の容器に分けて保管し、使用直前に混合することで、硬化性を向上させた二液タイプの製品が知られている。 Conventionally, condensation-curable, room-temperature-curable organopolysiloxane compositions have mainly been produced using organopolysiloxanes that are base polymers, in which both ends of the molecular chain are capped with silanol groups (hydroxyl groups bonded to silicon atoms). A one-component product that uses an organosilane compound with a hydrolyzable group as a crosslinking agent to cap the silanol group at the end of the molecular chain with a hydrolyzable silyl group and fills it in a sealed container, and a base polymer and hydrolyzable group. A two-component type product is known that improves curability by storing a crosslinking agent and a crosslinking agent in separate containers and mixing them immediately before use.
大気中の水分又は湿気による加水分解・縮合反応によって室温（２３℃±１５℃）でエラストマー状に硬化（架橋）する室温硬化性オルガノポリシロキサン組成物は、加水分解・縮合反応によって架橋剤から脱離して組成物外（系外）に放出される化合物のタイプによって大まかに分類され、種々のものが公知であるが、特に広く使用されているものとしては、加水分解・縮合反応によってメタノール等のアルコール化合物を放出する架橋剤を使用した脱アルコールタイプのものと、２－ブタノンオキシム等のオキシム化合物を放出する架橋剤を使用した脱オキシムタイプのものである。 A room-temperature-curable organopolysiloxane composition that cures (crosslinks) into an elastomer at room temperature (23°C ± 15°C) through a hydrolysis/condensation reaction caused by moisture or moisture in the air, can be released from a crosslinking agent by a hydrolysis/condensation reaction. They are roughly classified according to the type of compound that is released outside the composition (outside the system), and various types are known, but the most widely used ones are those that release methanol etc. through hydrolysis and condensation reactions One is a dealcoholization type that uses a crosslinking agent that releases an alcohol compound, and the other is an oxime removal type that uses a crosslinking agent that releases an oxime compound such as 2-butanone oxime.
これらの架橋剤を使用した縮合硬化型の室温硬化性オルガノポリシロキサン組成物を硬化して得られる硬化物（シリコーンゴム硬化物）は、耐久性やゴム物性、各種の基材に対する接着性などに優れ、すでに建築分野、自動車分野、電気電子分野など幅広い用途にすでに使用されている。 The cured product (silicone rubber cured product) obtained by curing a condensation-curable, room-temperature-curable organopolysiloxane composition using these crosslinking agents has excellent durability, rubber physical properties, and adhesion to various substrates. It is excellent and has already been used in a wide range of applications, including the architectural, automotive, and electrical and electronic fields.
一方で、これらの組成物では、湿気硬化時に放出される脱離基（脱離化合物）が、劇物であるメタノールや、発がん性を疑われる２－ブタノンオキシムなどであり、近年の作業員の安全性確保や環境保護の観点から、より安全性の高い脱離基（脱離化合物）に代替することが求められている。 On the other hand, in these compositions, the leaving groups (eliminating compounds) released during moisture curing include methanol, which is a deleterious substance, and 2-butanone oxime, which is suspected to be carcinogenic. From the viewpoint of ensuring safety and protecting the environment, there is a need to substitute leaving groups (leaving compounds) with higher safety.
特表２０１８－５１５６３４号公報では、脱アルコール型、脱オキシム型架橋剤の代替として、乳酸エチル等を代表とするα－ヒドロキシカルボン酸エステル化合物を脱離・放出するシラン化合物を架橋剤として含有する縮合硬化型オルガノポリシロキサン組成物を提案している。こちらの系では脱離基である乳酸エチルは安全性の高い化合物である一方、縮合触媒として有機錫系触媒の使用を必須としているが、該有機錫系触媒は水生生物等に対する有害性が指摘されているため環境保護の観点から好ましくない。 According to Japanese Patent Publication No. 2018-515634, as a substitute for dealcohol type and deoxime type cross-linking agents, a silane compound that desorbs and releases an α-hydroxycarboxylic acid ester compound represented by ethyl lactate etc. is contained as a cross-linking agent. A condensation-curable organopolysiloxane composition is proposed. In this system, while the leaving group ethyl lactate is a highly safe compound, it is essential to use an organotin catalyst as a condensation catalyst, but it has been pointed out that the organotin catalyst is harmful to aquatic organisms. This is not desirable from an environmental protection perspective.
特公昭５１－３９６７３号公報では、アセトンを代表とするケトン系化合物を放出する縮合硬化型オルガノポリシロキサン組成物を提案している。アセトンは２－ブタノンオキシムやメタノールと比較して、人体に対して有害性の低い化合物であり、さらに従来の硬化システムよりも速硬化で、かつ耐久性に優れるシリコーンゴム硬化物を与える組成物を提供している。しかし、アセトンの引火点は－２０℃と低く、揮発性が高いため、使用環境に制限があるという問題がある。 Japanese Patent Publication No. 51-39673 proposes a condensation-curable organopolysiloxane composition that releases a ketone compound typified by acetone. Acetone is a compound that is less harmful to the human body than 2-butanone oxime and methanol, and we have developed a composition that provides cured silicone rubber products that cure faster and are more durable than conventional curing systems. providing. However, acetone has a low flash point of -20°C and is highly volatile, so there is a problem that there are restrictions on the environment in which it can be used.
特公平６－８６５７２号公報では、鎖長延長剤としてアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を放出する２官能性のシランカップリング剤を使用した縮合硬化型オルガノポリシロキサン組成物を提案しているが、この報告例の組成物では３次元の架橋構造を形成してエラストマー硬化物を得るために、メタノールや２－ブタノンオキシムを放出する既存の３官能性以上の脱アルコール型や脱オキシム型の架橋剤が必要となる。 Japanese Patent Publication No. 6-86572 discloses a condensation-curable organopolysiloxane composition using a bifunctional silane coupling agent that releases a β-ketoester compound such as acetoacetate or malonic acid ester as a chain extender. However, in order to form a three-dimensional crosslinked structure and obtain a cured elastomer, the composition in this report uses the existing trifunctional or higher-functional dealcoholization type that releases methanol or 2-butanone oxime. A deoxime type crosslinking agent is required.
本発明は、上記事情に鑑みなされたもので、加水分解・縮合反応の際に、安全性に優れた脱離基（脱離化合物）である、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を放出しながら、良好なゴム物性、速硬化性を与える室温硬化性オルガノポリシロキサン組成物を与えることができる架橋剤として有用な、新規の加水分解性オルガノシラン化合物及び室温硬化性オルガノポリシロキサン組成物の架橋剤を提供することを目的とするものである。
The present invention has been made in view of the above circumstances, and is based on β-ketoesters such as acetoacetate and malonate, which are leaving groups (elimination compounds) with excellent safety during hydrolysis and condensation reactions. Novel hydrolyzable organosilane compounds and room-temperature-curable organopolysiloxanes useful as crosslinking agents capable of providing room-temperature-curable organopolysiloxane compositions that exhibit good rubber physical properties and fast curing properties while releasing compounds. The object is to provide a crosslinking agent for compositions .
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、加水分解によって、人体にとって毒性の低い、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を放出する有機ケイ素化合物（加水分解性オルガノシラン化合物）が、室温硬化性オルガノポリシロキサン組成物の架橋剤として適用した場合に、安全性に優れ、従来の硬化タイプ（脱アルコールタイプや脱オキシムタイプ）の室温硬化性オルガノポリシロキサン組成物と同等以上のゴム物性及び速硬化性を発現する室温硬化性オルガノポリシロキサン組成物を与えることができることを見出し、本発明をなすに至った。 As a result of extensive studies to achieve the above object, the present inventors discovered that an organosilicon compound (hydrated When a degradable organosilane compound (degradable organosilane compound) is applied as a crosslinking agent in a room-temperature-curable organopolysiloxane composition, it has excellent safety and can be used as a room-temperature-curable organopolysiloxane of the conventional curing type (dealcoholization type or deoxime type). The present inventors have discovered that it is possible to provide a room-temperature-curable organopolysiloxane composition that exhibits rubber physical properties and rapid curing properties that are equal to or better than those of the composition, and the present invention has been completed.
即ち、本発明は、室温硬化性オルガノポリシロキサン組成物の架橋剤（硬化剤）として有用な下記の新規加水分解性オルガノシラン化合物、及び室温硬化性オルガノポリシロキサン組成物の架橋剤を提供するものである。
［１］
下記一般式（１）で示される加水分解性オルガノシラン化合物。
［２］
加水分解によってβ－ケトエステル化合物を脱離するものである［１］に記載の加水分解性オルガノシラン化合物。
［３］
β－ケトエステル化合物が、アセト酢酸エチル又はマロン酸ジエチルである［２］に記載の加水分解性オルガノシラン化合物。
［４］
室温硬化性オルガノポリシロキサン組成物の架橋剤用である［１］～［３］のいずれかに記載の加水分解性オルガノシラン化合物。
［５］
［１］～［３］のいずれかに記載の加水分解性オルガノシラン化合物からなる室温硬化性オルガノポリシロキサン組成物の架橋剤。
That is, the present invention provides the following novel hydrolyzable organosilane compounds useful as crosslinking agents (curing agents) for room-temperature-curable organopolysiloxane compositions, and cross-linking agents for room-temperature-curable organopolysiloxane compositions. It is.
[1]
A hydrolyzable organosilane compound represented by the following general formula (1).
[2]
The hydrolysable organosilane compound according to [1], which eliminates the β-ketoester compound by hydrolysis.
[3]
The hydrolyzable organosilane compound according to [2] , wherein the β-ketoester compound is ethyl acetoacetate or diethyl malonate.
[4]
The hydrolyzable organosilane compound according to any one of [1] to [3], which is used as a crosslinking agent for a room-temperature curable organopolysiloxane composition.
[5]
A crosslinking agent for a room temperature-curable organopolysiloxane composition comprising the hydrolyzable organosilane compound according to any one of [1] to [3].
このような加水分解によって生じる脱離基（脱離化合物）として、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離する有機ケイ素化合物（加水分解性オルガノシラン化合物）を室温硬化性オルガノポリシロキサン組成物の架橋剤（硬化剤）として用いれば、特に速硬化性を有し、ゴム物性に優れた硬化物を与えるものとすることができる。 As a leaving group (elimination compound) generated by such hydrolysis, an organosilicon compound (hydrolyzable organosilane compound) that leaves β-ketoester compounds such as acetoacetate and malonate is used as a room-temperature curable organosilane compound. When used as a crosslinking agent (curing agent) for a polysiloxane composition, it can provide a cured product that has particularly fast curing properties and has excellent rubber physical properties.
なお、前記加水分解性オルガノシラン化合物において、加水分解によって生じる脱離基（脱離化合物）が、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸アリル、アセト酢酸フェニル、アセト酢酸ベンジル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジプロピル、マロン酸ジペンチル、マロン酸ジアリル、マロン酸ジフェニル、マロン酸ジベンジル等のβ－ケトエステル化合物であることが好ましい。これらの化合物は、一部食品添加物や香料として使用されていることから、安全性の高い化合物である。 In addition, in the hydrolyzable organosilane compound, the leaving group (leaving compound) generated by hydrolysis is methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, allyl acetoacetate, phenyl acetoacetate, benzyl acetoacetate, malon. β-ketoester compounds such as dimethyl acid, diethyl malonate, dipropyl malonate, dipentyl malonate, diallyl malonate, diphenyl malonate, and dibenzyl malonate are preferred. These compounds are highly safe because they are partially used as food additives and flavoring agents.
本発明の加水分解性オルガノシラン化合物は、脱離基（脱離化合物）としてより安全性の高い化合物を放出し、特に室温硬化性オルガノポリシロキサン組成物の架橋剤として使用した場合に、該組成物は、硬化性に優れ、空気中に曝すと速やかに硬化して、優れた物性を示すことから、この加水分解性オルガノシラン化合物を含む組成物は、建築用途、自動車用途、電気電子用接着剤用途として有効に使用することができる。 The hydrolyzable organosilane compound of the present invention releases a safer compound as a leaving group (elimination compound), and particularly when used as a crosslinking agent for a room-temperature curable organopolysiloxane composition, The compound has excellent curability, hardens quickly when exposed to air, and exhibits excellent physical properties. Therefore, compositions containing this hydrolyzable organosilane compound are suitable for architectural applications, automotive applications, and adhesives for electrical and electronic applications. It can be effectively used as a drug.
以下、本発明について詳細に説明する。 The present invention will be explained in detail below.
本発明の加水分解性オルガノシラン化合物は、下記一般式（１）で示される、加水分解によって生じる脱離基（脱離化合物）として、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を脱離する有機ケイ素化合物（加水分解性オルガノシラン化合物）である。
ここで、上記一般式（１）において、Ｒ1は炭素数１～１０、好ましくは炭素数１～６の１価脂肪族炭化水素基、炭素数６～１０のアリール基又は炭素数７～１０のアラルキル基であり、このＲ1としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基などを例示することができる。これらの中でも、メチル基、ビニル基、フェニル基が好ましく、メチル基、ビニル基が特に好ましい。 Here, in the above general formula (1), R 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms. This R 1 is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2 - Alkyl groups such as ethylhexyl, nonyl and decyl groups, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl and butenyl groups, aryl groups such as phenyl and tolyl groups, benzyl groups and phenylethyl groups Examples include aralkyl groups such as. Among these, methyl group, vinyl group, and phenyl group are preferred, and methyl group and vinyl group are particularly preferred.
上記一般式（１）において、Ｒ2はエーテル結合酸素原子を有していてもよい炭素数１～１０、好ましくは炭素数１～６の炭化水素基、エーテル結合酸素原子を有していてもよい炭素数６～１０のアリール基又はエーテル結合酸素原子を有していてもよい炭素数７～１０のアラルキル基であり、このＲ2としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等のアルコキシ基、ビニルオキシ基、アリルオキシ基、プロペノキシ基、イソプロペノキシ基等のアルケニルオキシ基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、フェノキシ基等のアリールオキシ基、ベンジルオキシ基、フェニルエチルオキシ基等のアラルキルオキシ基などを例示することができる。これらの中でも、メチル基、エチル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、アリルオキシ基、フェノキシ基、ベンジルオキシ基が好ましく、メチル基、エトキシ基が特に好ましい。 In the above general formula (1), R 2 is a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may have an ether-bonded oxygen atom, or a hydrocarbon group having an ether-bonded oxygen atom. It is preferably an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms which may have an ether-bonded oxygen atom, and R 2 is a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, vinyl group, allyl group, propenyl group, iso Alkenyl groups such as propenyl group and butenyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, etc. , alkenyloxy groups such as vinyloxy group, allyloxy group, propenoxy group, isopropenoxy group, aryl group such as phenyl group and tolyl group, aralkyl group such as benzyl group and phenylethyl group, aryloxy group such as phenoxy group, benzyloxy group , aralkyloxy groups such as phenylethyloxy groups, and the like. Among these, methyl group, ethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, allyloxy group, phenoxy group, and benzyloxy group are preferable, and methyl group and ethoxy group are particularly preferable.
上記一般式（１）において、Ｒ3は炭素数１～１０、好ましくは炭素数１～６の１価脂肪族炭化水素基、炭素数６～１０のアリール基又は炭素数７～１０のアラルキル基であり、このＲ3としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基などを例示することができる。これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、アリル基、フェニル基、ベンジル基が好ましく、メチル基、エチル基が特に好ましい。 In the above general formula (1), R 3 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. and this R 3 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. , alkyl groups such as nonyl group, decyl group, alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, aryl group such as phenyl group, tolyl group, aralkyl group such as benzyl group, phenylethyl group, etc. Examples include groups. Among these, methyl group, ethyl group, propyl group, butyl group, pentyl group, allyl group, phenyl group, and benzyl group are preferable, and methyl group and ethyl group are particularly preferable.
また、上述したとおり、ｎは３又は４である。この数が３未満である場合は架橋反応によるゴム硬化が起こらず、縮合硬化型室温硬化性オルガノポリシロキサン組成物の架橋剤として不適である。 Moreover, as mentioned above, n is 3 or 4. When this number is less than 3, rubber curing due to crosslinking reaction does not occur, making it unsuitable as a crosslinking agent for a condensation-curable room-temperature-curable organopolysiloxane composition.
本発明の加水分解性オルガノシラン化合物は、例えば、クロロシランとアセト酢酸エステルもしくはマロン酸エステル等のβ－ケトエステル化合物を塩基性物質の存在下に反応（例えば脱塩酸反応）させることで製造できる。この反応式は、例えば下記式［１］で表される。 The hydrolysable organosilane compound of the present invention can be produced, for example, by reacting chlorosilane with a β-ketoester compound such as acetoacetate or malonic acid ester in the presence of a basic substance (for example, dehydrochlorination reaction). This reaction formula is expressed, for example, by the following formula [1].
ここで、クロロシランとしては、下記に示すものが例示できる。
また、β－ケトエステル化合物としては、下記に示すアセト酢酸エステル、マロン酸エステル等が例示できる。これらの化合物は比較的安価であり、一部食品添加物や香料として使用されていることから、安全性の高い化合物である。
クロロシランと反応させるアセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物の添加量は、クロロシラン中の塩素原子数１モルに対して、０．９５モル～２．０モルが好ましく、０．９９～１．５モルが特に好ましく、１．０～１．２モルがさらに好ましい。β－ケトエステル化合物の添加量が少ないと反応が終結しないおそれがあり、β－ケトエステル化合物の添加量が多すぎると精製に時間がかかり、製造時間が増加してしまう。 The amount of β-ketoester compounds such as acetoacetic ester and malonic acid ester to be reacted with chlorosilane is preferably 0.95 mol to 2.0 mol, and 0.99 to 2.0 mol per mol of chlorine atoms in chlorosilane. 1.5 mol is particularly preferred, and 1.0 to 1.2 mol is even more preferred. If the amount of the β-keto ester compound added is too small, the reaction may not be completed, and if the amount of the β-keto ester compound added is too large, purification will take time and the production time will increase.
反応に使用する塩基性物質としては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、尿素、ジアザビシクロウンデセン、ジアザビシクロノネンなどの求核性の低い塩基性物質が使用できる。この中でもトリメチルアミン、トリエチルアミン、トリブチルアミンが好ましく、特にトリエチルアミンが好ましい。
塩基性物質の添加量としては、クロロシラン中の塩素原子数１モルに対して０．９５モル～２．０モルが好ましく、０．９９～１．５モルが特に好ましく、１．０～１．２モルがさらに好ましい。塩基添加量が少ないと反応が終結しないおそれがあり、塩基添加量が多すぎると経済的に不利である。
As the basic substance used in the reaction, basic substances with low nucleophilicity such as trimethylamine, triethylamine, tripropylamine, tributylamine, urea, diazabicycloundecene, and diazabicyclononene can be used. Among these, trimethylamine, triethylamine, and tributylamine are preferred, and triethylamine is particularly preferred.
The amount of the basic substance added is preferably 0.95 to 2.0 moles, particularly preferably 0.99 to 1.5 moles, and particularly preferably 1.0 to 1.0 moles per mole of chlorine atoms in the chlorosilane. 2 mol is more preferred. If the amount of base added is too small, the reaction may not be completed, and if the amount of base added is too large, it is economically disadvantageous.
本発明の加水分解性オルガノシラン化合物の製造には、一般に使用される溶剤を使用してもよく、例えば、トルエン、キシレン、ベンゼン等の芳香族炭化水素類、ペンタン、ヘキサン、ヘプタン、ノナン、オクタン、デカンなどの脂肪族炭化水素類、ジメチルエーテル、メチルエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類、パークロロエタン、パークロロエチレン、トリクロロエタン、クロロホルム、四塩化炭素などのハロゲン化炭化水素、ジメチルホルムアミドなどのアミド類、酢酸エチル、酢酸メチル、酢酸ブチルなどのエステル類などの有機溶剤が挙げられる。
溶剤の使用量としては特に限定されないが、通常、使用するβ－ケトエステル化合物１００質量部に対して、１０～５００質量部、好ましくは３０～３００質量部、より好ましくは５０～２００質量部等の範囲で使用される。
In the production of the hydrolyzable organosilane compound of the present invention, commonly used solvents may be used, such as aromatic hydrocarbons such as toluene, xylene, benzene, pentane, hexane, heptane, nonane, octane, etc. , aliphatic hydrocarbons such as decane, ethers such as dimethyl ether, methyl ethyl ether, tetrahydrofuran, and dioxane, halogenated hydrocarbons such as perchloroethane, perchloroethylene, trichloroethane, chloroform, and carbon tetrachloride, and amides such as dimethylformamide. Examples include organic solvents such as esters such as ethyl acetate, methyl acetate, and butyl acetate.
The amount of the solvent used is not particularly limited, but is usually 10 to 500 parts by weight, preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight, etc., per 100 parts by weight of the β-ketoester compound used. used in range.
クロロシランとβ－ケトエステル化合物との反応条件としては、通常、０～８０℃、好ましくは０～６０℃でクロロシランにβ－ケトエステル化合物を滴下し、３０～８０℃、好ましくは４０～６０℃で１～４８時間、好ましくは３～３０時間程度反応させることが好ましい。反応時の温度が低すぎると反応が完結しない場合があり、温度が高すぎると生成物の着色が大きくなる場合がある。また、反応時間が短すぎると反応が完結しない場合があり、反応時間が長すぎると生産性に不利に働く。また、反応終了後の精製は減圧環境下で加熱することで、未反応物及び溶剤を留去することで可能であり、減圧度は好ましくは０～３，０００Ｐａ、より好ましくは０～２，０００Ｐａであり、温度は好ましくは５０～１５０℃、より好ましくは７０～１２０℃である。減圧度が高すぎると未反応物、溶剤の留去が困難となる場合がある。また、精製時の温度が低すぎると、未反応物、溶剤の留去が困難となる場合があり、高すぎると反応物の着色や分解を招くおそれがある。 The reaction conditions for the chlorosilane and the β-ketoester compound are usually such that the β-ketoester compound is added dropwise to the chlorosilane at 0 to 80°C, preferably 0 to 60°C, and the β-ketoester compound is added dropwise to the chlorosilane at 30 to 80°C, preferably 40 to 60°C. It is preferable to react for about 48 hours, preferably about 3 to 30 hours. If the temperature during the reaction is too low, the reaction may not be completed; if the temperature is too high, the product may become heavily colored. Moreover, if the reaction time is too short, the reaction may not be completed, and if the reaction time is too long, it will work against productivity. Further, purification after the completion of the reaction is possible by distilling off unreacted substances and solvent by heating in a reduced pressure environment, and the degree of reduced pressure is preferably 0 to 3,000 Pa, more preferably 0 to 2,000 Pa. 000 Pa, and the temperature is preferably 50 to 150°C, more preferably 70 to 120°C. If the degree of vacuum is too high, it may be difficult to distill off unreacted substances and solvent. Furthermore, if the temperature during purification is too low, it may be difficult to distill off unreacted substances and solvents, and if the temperature is too high, there is a risk of coloring or decomposition of the reactants.
本発明の加水分解性オルガノシラン化合物の具体例としては、例えば、下記式で表されるものが挙げられる。
本発明の加水分解性オルガノシラン化合物は、加水分解によって生じる脱離基（脱離化合物）が、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸アリル、アセト酢酸フェニル、アセト酢酸ベンジル等のアセト酢酸エステル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジプロピル、マロン酸ジペンチル、マロン酸ジアリル、マロン酸ジフェニル、マロン酸ジベンジル等のマロン酸エステルなどのβ－ケトエステル化合物であることが好ましく、特に好ましくはアセト酢酸エチル、マロン酸ジエチルである。これらの化合物は、食品添加物や香料として使用されており、安全性の高い化合物である。 The hydrolyzable organosilane compound of the present invention has a leaving group (eliminating compound) generated by hydrolysis such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, allyl acetoacetate, phenyl acetoacetate, benzyl acetoacetate, etc. β-ketoester compounds such as malonic acid esters such as acetoacetate, dimethyl malonate, diethyl malonate, dipropyl malonate, dipentyl malonate, diallyl malonate, diphenyl malonate, and dibenzyl malonate are preferred, and particularly preferred. are ethyl acetoacetate and diethyl malonate. These compounds are used as food additives and flavoring agents, and are highly safe compounds.
本発明の新規加水分解性オルガノシラン化合物は、加水分解によって生じる脱離基（脱離化合物）として、アセト酢酸エステルもしくはマロン酸エステルを有し、室温硬化性オルガノポリシロキサン組成物の架橋剤として使用される。 The novel hydrolyzable organosilane compound of the present invention has an acetoacetate or malonic acid ester as a leaving group (leaving compound) generated by hydrolysis, and is used as a crosslinking agent for room temperature-curable organopolysiloxane compositions. be done.
室温硬化性オルガノポリシロキサン組成物の架橋剤として、このような加水分解性オルガノシラン化合物であれば、より高い安全性、速硬化性を付与することができる。
加水分解によって生じる脱離基（脱離化合物）として、より安全性の高い、アセト酢酸エステル、マロン酸エステル等のβ－ケトエステル化合物を放出する加水分解性オルガノシラン化合物を架橋剤（硬化剤）として使用することによって、ゴム物性に優れた硬化物を与え、速硬化性を有する縮合硬化型室温硬化性オルガノシロキサン組成物が得られる。
If such a hydrolyzable organosilane compound is used as a crosslinking agent for a room-temperature-curable organopolysiloxane composition, higher safety and faster curing properties can be imparted.
Hydrolyzable organosilane compounds that release β-ketoester compounds such as acetoacetate and malonate, which are safer, are used as crosslinking agents (curing agents) as leaving groups (elimination compounds) generated by hydrolysis. When used, a condensation-curable room-temperature-curable organosiloxane composition that provides a cured product with excellent rubber physical properties and has rapid curing properties can be obtained.
以下、実施例、合成参考例、参考例及び比較参考例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の具体例において、「部」は「質量部」を意味する。粘度は回転粘度計による２３℃での測定値である。
EXAMPLES Hereinafter, the present invention will be specifically explained by showing Examples , Synthesis Reference Examples, Reference Examples , and Comparative Reference Examples, but the present invention is not limited to the following Examples. In addition, in the following specific examples, "part" means "part by mass." The viscosity is a value measured at 23°C using a rotational viscometer.
［実施例１］加水分解性オルガノシラン化合物１の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、アセト酢酸エチル３９０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でメチルトリクロロシラン１４８．７ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を９０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、アセト酢酸エチルを留去することで、加水分解性オルガノシラン化合物１を得た（収量３３５ｇ、収率７８％）。この反応式は、下記式［２］で表される。
［実施例２］加水分解性オルガノシラン化合物２の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、アセト酢酸エチル３９０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でビニルトリクロロシラン１６０．６ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を９０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、アセト酢酸エチルを留去することで、加水分解性オルガノシラン化合物２を得た（収量３４８ｇ、収率７８％）。この反応式は、下記式［３］で表される。
［実施例３］加水分解性オルガノシラン化合物３の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、アセト酢酸エチル３９０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でフェニルトリクロロシラン２１０．４ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を９０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、アセト酢酸エチルを留去することで、加水分解性オルガノシラン化合物３を得た（収量３５１ｇ、収率７１％）。この反応式は、下記式［４］で表される。
［合成参考例１］加水分解性オルガノシラン化合物４の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、アセト酢酸エチル３９０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でテトラクロロシラン１２６．７ｇ（０．７４６ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を９０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、アセト酢酸エチルを留去することで、加水分解性オルガノシラン化合物４を得た（収量２５８ｇ、収率６３％）。この反応式は、下記式［５］で表される。
［実施例４］加水分解性オルガノシラン化合物５の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、マロン酸ジエチル４８０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でメチルトリクロロシラン１４８．７ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を１２０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、マロン酸ジエチルを留去することで、加水分解性オルガノシラン化合物５を得た（収量２８０ｇ、収率５４％）。この反応式は、下記式［６］で表される。
［実施例５］加水分解性オルガノシラン化合物６の合成
機械攪拌機、温度計及び滴下ロートを備えた２，０００ｍＬの四つ口セパラブルフラスコに、マロン酸ジエチル４８０ｇ（３．０ｍｏｌ）、トリエチルアミン３０４ｇ（３．０ｍｏｌ）、ヘキサン８００ｍＬを仕込み、氷浴下でビニルトリクロロシラン１６０．６ｇ（０．９９５ｍｏｌ）を約２時間かけて滴下した。その後、４０℃で４時間撹拌後、生成したトリエチルアミン塩酸塩を濾過して取り除き、ろ液を１２０℃、３００Ｐａの条件でヘキサンと過剰のトリエチルアミン、マロン酸ジエチルを留去することで、加水分解性オルガノシラン化合物６を得た（収量２７１ｇ、収率５１％）。この反応式は、下記式［７］で表される。
［参考例１］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物１を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 1]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa・s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 1, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例２］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物２を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 2]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 2, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例３］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物３を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 3]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 3, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例４］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物４を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 4]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 4, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例５］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物５を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 5]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 5, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例６］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物６を１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 6]
100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 6, and 0.1 part of dioctyltin dilaurate were added, and the mixture was heated under moisture-blocking conditions. The composition was prepared by mixing until homogeneous.
［参考例７］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物１を１０部と、チタンジイソプロポキシビス（エチルアセトアセテート）３部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 7]
Added 100 parts of dimethylpolysiloxane with a viscosity of 50,000 mPa・s with both molecular chain ends capped with hydroxyl groups, 10 parts of hydrolyzable organosilane compound 1, and 3 parts of titanium diisopropoxy bis(ethyl acetoacetate). The composition was prepared by mixing until homogeneous under moisture protection.
［参考例８］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、加水分解性オルガノシラン化合物２を１０部加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference example 8]
Add 100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups and 10 parts of hydrolyzable organosilane compound 2, and mix until homogeneous under moisture exclusion to form a composition. Prepared.
［比較参考例１］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、ビニルトリスケトオキシムシランを１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Comparative reference example 1]
Add 100 parts of dimethylpolysiloxane with a viscosity of 50,000 mPa・s and whose molecular chain ends are capped with hydroxyl groups, 10 parts of vinyltrisketoxime silane, and 0.1 part of dioctyltin dilaurate, and mix uniformly under moisture protection. A composition was prepared by mixing until the mixture was mixed.
［比較参考例２］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、ビニルトリメトキシシランを１０部と、ジオクチル錫ジラウレート０．１部を加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Comparative reference example 2]
Add 100 parts of dimethylpolysiloxane with a viscosity of 50,000 mPa・s with both molecular chain ends capped with hydroxyl groups, 10 parts of vinyltrimethoxysilane, and 0.1 part of dioctyltin dilaurate, and homogenize under moisture protection. A composition was prepared.
［比較参考例３］
粘度５０，０００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と、ビニルトリメトキシシランを１０部加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Comparative reference example 3]
A composition was prepared by adding 100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa·s and having both molecular chain ends capped with hydroxyl groups and 10 parts of vinyltrimethoxysilane, and mixing the mixture until homogeneous under moisture exclusion.
上記参考例、比較参考例で調製された組成物を２ｍｍの型枠に流し込み、２３℃、５０％ＲＨで７日間養生して２ｍｍ厚のゴムシートを得た。ＪＩＳ Ａ ５７５８に規定する方法に準じてタックフリータイム（指触乾燥時間）を測定し、ＪＩＳ Ｋ ６２４９に準じて２ｍｍ厚シートよりゴム物性（硬さ、切断時伸び、引張り強度）を測定した。
これらの結果を下記表１に示した。
The compositions prepared in the above reference examples and comparative reference examples were poured into a 2 mm mold and cured at 23° C. and 50% RH for 7 days to obtain a 2 mm thick rubber sheet. Tack-free time (touch dry time) was measured according to the method specified in JIS A 5758, and rubber physical properties (hardness, elongation at cutting, tensile strength) were measured from a 2 mm thick sheet according to JIS K 6249.
These results are shown in Table 1 below.
本発明の加水分解性オルガノシラン化合物は、錫触媒系、チタン触媒系、そして触媒不使用の系でも問題なく硬化し、錫触媒を使用した参考例１～６の組成物では、錫触媒を使用した脱オキシム型である比較参考例１の組成物と同等以上の硬化性を示した。一方で脱アルコールタイプである比較参考例２、３の組成物では、タックフリータイムが遅く、触媒未添加である比較参考例３の組成物では硬化しなかった。また、参考例１～８の組成物では、硬化時に脱離するガスはアセト酢酸エチル、マロン酸ジエチルと安全性の高い化合物であり、発がん性が疑われる２－ブタノンオキシムを放出する比較参考例１の組成物や、劇物であるメタノールを放出する比較参考例２、３の組成物と比べて安全面でも有利である。 The hydrolyzable organosilane compound of the present invention is cured without problems in a tin catalyst system, a titanium catalyst system, and a catalyst-free system, and the compositions of Reference Examples 1 to 6 using a tin catalyst use a tin catalyst. The composition exhibited curability equivalent to or higher than that of the composition of Comparative Reference Example 1, which is an oxime-free type. On the other hand, the compositions of Comparative Reference Examples 2 and 3, which are dealcoholization types, had slow tack-free times, and the composition of Comparative Reference Example 3, in which no catalyst was added, did not cure. In addition, in the compositions of Reference Examples 1 to 8, the gases released during curing are highly safe compounds such as ethyl acetoacetate and diethyl malonate, and comparative reference examples release 2-butanone oxime, which is suspected to be carcinogenic. It is also advantageous in terms of safety compared to composition No. 1 and the compositions of Comparative Reference Examples 2 and 3, which emit methanol, which is a deleterious substance.
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