WO2023054052A1 - 接合部材の解体方法及び接合部材並びに易解体性の液状シリコーン系接着剤 - Google Patents
接合部材の解体方法及び接合部材並びに易解体性の液状シリコーン系接着剤 Download PDFInfo
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- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 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 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- NHWNGVQMIQXKCB-UHFFFAOYSA-N dimethoxy(dimethyl)stannane Chemical compound CO[Sn](C)(C)OC NHWNGVQMIQXKCB-UHFFFAOYSA-N 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- DWCFFYWHRSPCAT-UHFFFAOYSA-N ethenyl-tris(ethoxymethoxy)silane Chemical compound CCOCO[Si](OCOCC)(OCOCC)C=C DWCFFYWHRSPCAT-UHFFFAOYSA-N 0.000 description 1
- SXPRUADRKCDQDZ-UHFFFAOYSA-N ethenyl-tris(methoxymethoxy)silane Chemical compound COCO[Si](OCOC)(OCOC)C=C SXPRUADRKCDQDZ-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- LJXHBYMNJWXSQV-UHFFFAOYSA-N ethyl-tris(methoxymethoxy)silane Chemical compound C(C)[Si](OCOC)(OCOC)OCOC LJXHBYMNJWXSQV-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZKWONARDNQWFKT-UHFFFAOYSA-N methanolate;titanium(2+) Chemical compound CO[Ti]OC ZKWONARDNQWFKT-UHFFFAOYSA-N 0.000 description 1
- ICCDZMWNLNRHGP-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-bis(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)CCCOCC1CO1 ICCDZMWNLNRHGP-UHFFFAOYSA-N 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UCFRVQXGPJMWPG-UHFFFAOYSA-N n-(2,6-dimethylheptan-4-ylidene)hydroxylamine Chemical compound CC(C)CC(=NO)CC(C)C UCFRVQXGPJMWPG-UHFFFAOYSA-N 0.000 description 1
- GFJAHEQHAFJVQN-UHFFFAOYSA-N n-[bis[acetyl(butyl)amino]-methylsilyl]-n-butylacetamide Chemical compound CCCCN(C(C)=O)[Si](C)(N(CCCC)C(C)=O)N(CCCC)C(C)=O GFJAHEQHAFJVQN-UHFFFAOYSA-N 0.000 description 1
- QGSHCFOSBYQBOL-UHFFFAOYSA-N n-[bis[acetyl(cyclohexyl)amino]-methylsilyl]-n-cyclohexylacetamide Chemical compound C1CCCCC1N(C(C)=O)[Si](C)(N(C1CCCCC1)C(C)=O)N(C(=O)C)C1CCCCC1 QGSHCFOSBYQBOL-UHFFFAOYSA-N 0.000 description 1
- HXTZZFBBMWUFFG-UHFFFAOYSA-N n-[bis[acetyl(methyl)amino]-methylsilyl]-n-methylacetamide Chemical compound CC(=O)N(C)[Si](C)(N(C)C(C)=O)N(C)C(C)=O HXTZZFBBMWUFFG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical group CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Chemical class 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 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
- FRTIMPBIIJFDKJ-UHFFFAOYSA-N tetrakis(ethoxymethyl) silicate Chemical compound C(C)OCO[Si](OCOCC)(OCOCC)OCOCC FRTIMPBIIJFDKJ-UHFFFAOYSA-N 0.000 description 1
- XWURSMLUVXNFAE-UHFFFAOYSA-N tetrakis(methoxymethyl) silicate Chemical compound COCO[Si](OCOC)(OCOC)OCOC XWURSMLUVXNFAE-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- BIORFXJFONBLHK-UHFFFAOYSA-N tris(ethoxymethoxy)-ethylsilane Chemical compound CCOCO[Si](CC)(OCOCC)OCOCC BIORFXJFONBLHK-UHFFFAOYSA-N 0.000 description 1
- XLZISTYEMHIFPU-UHFFFAOYSA-N tris(ethoxymethoxy)-phenylsilane Chemical compound C1(=CC=CC=C1)[Si](OCOCC)(OCOCC)OCOCC XLZISTYEMHIFPU-UHFFFAOYSA-N 0.000 description 1
- SIPZPYIWLGBADC-UHFFFAOYSA-N tris(methoxymethoxy)-methylsilane Chemical compound C[Si](OCOC)(OCOC)OCOC SIPZPYIWLGBADC-UHFFFAOYSA-N 0.000 description 1
- YCHFCMARLOQJGL-UHFFFAOYSA-N tris(methoxymethoxy)-phenylsilane Chemical compound C1(=CC=CC=C1)[Si](OCOC)(OCOC)OCOC YCHFCMARLOQJGL-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to the dismantling of joining members using a curable liquid silicone adhesive that enables the collection, repair, and recycling of automobile parts such as automobile electrical parts and electric/electronic products to be easily carried out in a short period of time.
- the present invention relates to a method, a joining member used in the method, and an easily dismantling liquid silicone adhesive.
- Patent Document 1 Japanese Patent Laid-Open No. 2003-026784
- Patent Document 1 describes joining members using a polyol-based curable composition at 150 to 200 It has been proposed to soften or liquefy the material by heating it to 10° C. and dismantle the members joined by the cured material. Further, in Japanese Patent Application Laid-Open No.
- Patent Document 2 by bringing a halogen-based organic solvent into contact with a bonding portion of an adhesive structure using a moisture-curable adhesive containing a urethane prepolymer as a main component, , it has been proposed to detach the constituent members of the adhesive structure from the adhesive portion after reducing the adhesive strength of the adhesive portion. Furthermore, in Japanese Patent Laid-Open No. 2008-120903 (Patent Document 3), an adhesive made of a vinyl-based monomer mixture containing alkyl (meth)acrylate as a main component is used, and a high normal state adhesive strength is maintained during bonding.
- Patent Document 4 proposes that rework is possible by incorporating a tackifier resin into an oxyalkylene polymer, rebonding is possible after rework, and sealing performance can be maintained. ing.
- silicone-based adhesives and sealants are widely used in the fields of automobiles, electrical and electronics, construction, etc., because they have better properties such as heat resistance and weather resistance than the above organic adhesives.
- silicone-based adhesives and sealants are difficult to decompose even when heated, there is a problem that it is difficult to repair or recycle them.
- a masking-type silicone adhesive has been proposed as a silicone adhesive that facilitates the dismantling of members and can exhibit sealing properties.
- Masking-type silicone adhesives containing no tackifier include silicone adhesives to which a release agent is added to impart releasability to glass and metal.
- the detachability imparting agent itself is thermally decomposed and loses its effectiveness when subjected to high-temperature durability exceeding 200° C., and the member and the silicone-based adhesive are adhered by heat, making it difficult to dismantle. Difficult to collect and repair.
- JP 2003-026784 A JP-A-2002-327163 Japanese Patent Application Laid-Open No. 2008-120903 Japanese Patent No. 6221630 Japanese Patent Application No. 2021-090750
- the present invention has been made in view of the above circumstances, and the bonded adhesive member is a silicone-based adhesive, and is exposed to a high temperature of about 150°C at room temperature (23°C ⁇ 15°C, the same applies hereinafter).
- a method for dismantling the joining member, and an easily dismantling liquid silicone adhesive used for the joining member intended to provide a joining member that can be easily recycled in a short time and with little energy consumption while exhibiting sealing performance afterward.
- Patent Document 5 Japanese Patent Application No. 2021-090750
- adding aluminum hydroxide that decomposes at around 160 ° C. to a curable liquid silicone adhesive in a specific proportion.
- the bonded adhesive members exhibit sealing properties even after being exposed to room temperature and further to a high temperature of about 150 ° C., and the sealing properties are reduced by exposing to a high temperature of 160 ° C. or higher.
- this method uses a heating furnace and heats for several hours, which consumes a large amount of energy.
- the present inventors have made intensive studies on joint members that consume less energy and can be recycled in a short time and their dismantling methods.
- a specific content of particles that generate heat by microwaves is added to the curable liquid silicone adhesive used as the bonding member for the bonding member, and furthermore, a hydroxide compound (especially A bonding member (particularly made of organic resin and/or metal, etc.) bonded with a cured product obtained by curing the curable liquid silicone adhesive by blending a metal hydroxide or a hydroxide of a metal oxide.
- a joint member in which a plurality of (particularly two) members are joined to each other) is exposed to room temperature and a high temperature of about 150 ° C.
- the present invention provides the following method for dismantling a joint member, the joint member, and an easily dismantleable liquid silicone adhesive.
- a curable liquid silicone adhesive containing particles that generate heat by microwaves and a hydroxide compound having a decomposition temperature of 180 to 600° C., and the content of the particles that generate heat by microwaves is 0.5 to 50% by mass.
- a bonding comprising a step of dismantling the bonding member by irradiating the cured product with microwaves to separate the plurality of members from each other and dismantle the bonding member, in which a plurality of members are bonded with a cured product obtained by curing the How to dismantle parts.
- the cured product of the curable liquid silicone adhesive is adhered by microwave irradiation while exhibiting adhesiveness and/or sealability from room temperature to a high temperature of about 150°C.
- a joining member that easily separates and joins a plurality of members, especially a plurality of (especially two) members made of organic resin and/or metal, etc., in a short time and with little energy consumption by reducing the strength and/or the sealing property. can be dismantled, the members can be easily recycled.
- the curable liquid silicone-based adhesive used as an adhesive member for the joining member is useful as an adhesive or sealing material for joints that require heat resistance and need to be recycled.
- the "heat-resistant temperature" of a member to be dismantled means the upper limit of the temperature at which the member does not thermally decompose or soften when the member is left at a specific temperature for 1 minute.
- the method for dismantling a joint member of the present invention contains particles that generate heat by microwaves and a hydroxide compound having a decomposition temperature of 180 to 600° C., and the content of the particles that generate heat by microwaves is 0.5 to 50 masses. %, by irradiating the cured product with microwaves, the plurality of members, especially those made of organic resin and/or a step of separating members made of metal or the like from each other to dismantle the joining members.
- the curable liquid silicone adhesive used in the present invention cures to become an adhesive member that joins a plurality of members, especially members made of organic resin and/or metal, etc., and generates heat by microwaves.
- the content of the particles (A) containing particles (A) and a hydroxide compound (B) having a decomposition temperature of 180 to 600 ° C. and generating heat by the microwave is 0.5 to 50% by mass
- the main chain is an adhesive using a polymer composed of siloxane bonds as a base polymer
- the curing type is preferably a condensation curing type or an addition reaction curing type.
- the particles (A) that generate heat by microwaves used in the present invention are the hydroxide compounds (especially metal hydroxides) blended in the curable liquid silicone adhesive as the particles generate heat when irradiated with microwaves. Hydroxides of substances or metal oxides) are decomposed, and water is generated with the decomposition of the hydroxide compounds, causing the adhesive to foam and the adhesive strength to decrease, so that it can be easily applied in a short time and with little energy consumption.
- the joining member can be dismantled.
- the present particles are particles that have the property of generating heat by microwaves in order to be dismantled. Particles with such properties are all preferable, but particles with a large dielectric constant have a high absorption rate of microwaves. It is more preferable because it is high and generates heat efficiently in a short time.
- the dielectric constant is preferably 3 to 1,000, more preferably 5 to 800 at 3 GHz.
- Particles that generate heat by microwaves are inorganic substances such as carbon such as acetylene black, furnace black, channel black, thermal black, Ketjen black, iron (II) oxide, iron (III) oxide, triiron tetraoxide and the like.
- Iron titanium oxide compounds such as titanium oxide (TiO), titanium dioxide (TiO 2 ), dititanium trioxide (Ti 2 O 3 ), ferrites such as spinel ferrite, magnetoplumbite ferrite, garnet ferrite, and silicon carbide At least one selected from the group is preferred, and among these, acetylene black, titanium dioxide, and silicon carbide are more preferred.
- the particles that generate heat by microwaves particles having an average particle diameter of preferably 0.05 to 100 ⁇ m, more preferably 0.1 to 80 ⁇ m are used. If the average particle size is less than 0.05 ⁇ m, the viscosity of the composition increases, so high filling may not be possible and sufficient heat generation effect may not be obtained. sexuality may be compromised.
- the average particle size can be obtained as a cumulative weight average value D50 (or median size) using a particle size distribution measuring device such as a laser beam diffraction method.
- the surface of the particles that generate heat by microwaves may be untreated or surface-treated (hydrophobic treatment).
- treating agents include alumina, silica, stearic acid, silane coupling agents, silicone compounds, and the like.
- Surface treatment can be performed by a known method.
- the treatment amount is not particularly limited, but it is preferably 10% by mass or less (usually 0.1 to 8% by mass), particularly 0.5 to 6% by mass.
- the particles that generate heat by microwaves can be used singly or in combination of two or more.
- the content of particles that generate heat by microwaves is 0.5 to 50% by mass, preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and even more preferably 3 to 30% by mass, based on the total curable liquid silicone adhesive. 5 to 20% by mass. If the amount is less than 0.5% by mass, sufficient heat generation cannot be obtained, and if the amount exceeds 50% by mass, the viscosity of the composition increases and the ejection properties during mixing and application deteriorate.
- the hydroxide compound (B) having a decomposition temperature of 180 to 600° C. is usually preferably a metal hydroxide or a metal oxide hydroxide, and aluminum hydroxide having a decomposition temperature of around 180° C.
- a metal hydroxide or a metal oxide hydroxide and aluminum hydroxide having a decomposition temperature of around 180° C.
- Magnesium hydroxide having a temperature of around 300°C and aluminum hydroxide oxide (boehmite) having a decomposition temperature of around 500°C can be mentioned.
- the decomposition begins to decompose when heated, and the decomposition generates water, which has an anti-inflammatory effect and is conventionally used as a flame-retardant material.
- the water generated by this decomposition is used to reduce the adhesive strength due to air bubbles generated in the cured product of the curable liquid silicone adhesive, thereby facilitating the dismantling of the joining member in a short time. can do.
- the hydroxide compound having a decomposition temperature of 180 to 600°C particles having an average particle size of 50 ⁇ m or less, preferably 0.5 to 20 ⁇ m are used. If the average particle size is more than 50 ⁇ m, the degradability will be lowered.
- the average particle size can be obtained as a cumulative weight average value D50 (or median size) using a particle size distribution measuring device such as a laser beam diffraction method.
- the surface of the hydroxide compound may be untreated or surface-treated (hydrophobic treatment).
- treating agents are generally used, and include silane coupling agents and fatty acids.
- Surface treatment can be performed by a known method.
- the treatment amount is not particularly limited, but it is preferably 3% by mass or less (usually 0.1 to 3% by mass), particularly 0.2 to 2% by mass.
- hydroxide compound may be used alone, two or more types having different average particle sizes and surface treatment methods may be used in combination.
- the content of the hydroxide compound is 35 to 65% by mass, preferably 40 to 60% by mass, more preferably 45 to 55% by mass, based on the total curable liquid silicone adhesive.
- the amount is less than 35% by mass, the decomposition (foaming) of the hydroxide compound is insufficient and the adhesive strength of the adhesive member does not decrease, and when the amount exceeds 65% by mass, the viscosity of the composition increases, and mixing and application are difficult. Dischargeability deteriorates at times.
- the total content of the particles (A) that generate heat by microwaves and the hydroxide compound (B) in the curable liquid silicone adhesive is preferably 36 to 85% by mass, more preferably 40 to 75% by mass, and 45% by mass.
- the mass ratio of the particles (A) that generate heat by microwaves and the hydroxide compound (B) is preferably 1:0.8 to 1:50, more preferably 1:1 to 1:30, and 1:2 to 1:20 is more preferred.
- Condensation-curable liquid silicone-based adhesives include (C) hydroxyl groups bonded to silicon atoms and (C) hydroxyl groups bonded to silicon atoms and / Or a linear diorganopolysiloxane (base polymer) having both ends of the molecular chain blocked with hydrolyzable silyl groups, (D) Hydrolysis having 3 or more hydrolyzable groups bonded to silicon atoms in the molecule Moisture (humidity) in the atmosphere at room temperature, including a reactive organosilane compound and / or a partial hydrolysis condensate thereof (crosslinking agent), (E) a curing catalyst, and (F) a silane coupling agent (adhesion imparting agent) It is a liquid silicone adhesive that obtains a cured product using the hydrolysis and condensation reaction of .
- Organopolysiloxane as the base polymer (main agent) is a linear diorganopolysiloxane blocked with hydroxyl groups (silanol groups) and/or hydrolyzable silyl groups bonded to silicon atoms at both ends of the molecular chain.
- the hydrolyzable silyl group is preferably an alkoxysilyl group or an alkoxy-substituted alkoxysilyl group.
- silicon-bonded hydroxyl group silanol group
- the hydrolyzable silyl group has an alkoxysilyl group or an alkoxy-substituted alkoxysilyl group at the terminal, an alkoxy group bonded to a silicon atom (that is, an alkoxysilyl group) or an alkoxy group bonded to a silicon atom is added to both ends of the molecular chain.
- alkoxyalkoxysilyl groups that is, dialkoxyorganosilyl groups or bis(alkoxyalkoxy)organosilyl groups, trialkoxysilyl groups or tris(alkoxyalkoxy)silyl existing as a base.
- the alkoxy group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy. , a hexyloxy group, an octyloxy group, and the like.
- the alkoxy-substituted alkoxy group is preferably an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group and the like.
- hydroxyl groups are particularly present at both ends of the diorganopolysiloxane, preferably only at both ends. (silanol group), methoxy group or ethoxy group is preferred.
- Examples of silicon-bonded organic groups other than hydroxyl groups and hydrolyzable groups include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
- Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, heptyl group, octyl group and 2-ethylhexyl group.
- cycloalkyl group such as cyclopentyl group and cyclohexyl group
- alkenyl group such as vinyl group and allyl group
- aryl group such as phenyl group, tolyl group and naphthyl group
- aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group ; those in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, or cyano groups, for example, halogenated groups such as trifluoropropyl group and chloropropyl group valent hydrocarbon group
- cyanoalkyl groups such as ⁇ -cyanoethyl group and ⁇ -cyanopropyl group are exemplified. Among them, a methyl group is preferred.
- the viscosity of the organopolysiloxane as the base polymer (main agent) at 23°C is preferably 50 to 1,000,000 mPa ⁇ s, more preferably 100 to 300,000 mPa ⁇ s. If the viscosity is less than the above lower limit, the cured product may not have sufficient mechanical properties, and if it exceeds the above upper limit, workability may be reduced. In the present invention, viscosity is a value at 23° C. measured by a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, rheometer, etc.) (same below).
- a rotational viscometer eg, BL type, BH type, BS type, cone plate type, rheometer, etc.
- the organopolysiloxane as the base polymer (main agent) may be used singly or in combination of two or more.
- the hydrolyzable organosilane compound and/or its partial hydrolysis condensate as a cross-linking agent is a hydrolyzable organosilane compound having three or more silicon-bonded hydrolyzable groups in the molecule. It is a silane compound and/or a partial hydrolysis condensate thereof (that is, a siloxane compound such as a siloxane oligomer having 3 or more residual hydrolyzable groups in the molecule).
- the hydrolyzable organosilane compound is a straight chain in which three or more hydrolyzable groups present in the molecule are blocked at both ends with hydroxyl groups and/or hydrolyzable silyl groups bonded to the silicon atoms of the base polymer. It acts as a cross-linking agent (curing agent) that forms a cross-linked structure through a hydrolysis/condensation reaction with diorganopolysiloxane.
- the hydrolyzable group possessed by the hydrolyzable organosilane compound includes an alkoxy group, an alkoxy-substituted alkoxy group, an acyloxy group, an alkenoxy group, a ketoxime group, an aminoxy group, and an amide group having 1 to 10 carbon atoms.
- alkoxy groups such as methoxy, ethoxy and propoxy groups
- alkoxy-substituted alkoxy groups such as methoxyethoxy, ethoxyethoxy and methoxypropoxy
- acyloxy groups such as acetoxy and octanoyloxy
- vinyloxy and isopropenoxy isopropenoxy.
- alkenoxy groups such as 1-ethyl-2-methylvinyloxy group
- ketoxime groups such as dimethylketoxime group, methylethylketoxime group and methylisobutylketoxime group
- aminoxy groups such as dimethylaminoxy group and diethylaminoxy group
- N- Examples include amide groups such as methylacetamide group and N-ethylacetamide group.
- the hydrolyzable organosilane compound may have an organic group bonded to a silicon atom other than the above hydrolyzable groups.
- Silicon-bonded organic groups other than such hydrolyzable groups include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. .
- alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, octadecyl group, etc.
- the unsubstituted or substituted monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group.
- hydrolyzable organosilane compounds and partial hydrolysis condensates thereof include methyltrimethoxysilane, ethyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Alkoxysilanes such as ethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane; methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, ethyltris(methylethylketoxime)silane, methyltris(methyl Ketooxime silanes such as isobutylketoxime)silane, vinyltris(methylethylketoxi
- the hydrolyzable organosilane compound used as a cross-linking agent does not have a monovalent hydrocarbon group substituted with a functional group having a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom in its molecule. In this point, it is clearly distinguished from (F) a silane coupling agent as an adhesiveness-imparting agent, which will be described later.
- the hydrolyzable organosilane compound and/or its partial hydrolysis condensate may be used singly or in combination of two or more.
- the amount of the hydrolyzable organosilane compound and/or its partial hydrolyzed condensate as a cross-linking agent (curing agent) is such that both ends of the molecular chain are blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. It is 0.1 to 40 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of linear diorganopolysiloxane. If the amount of the hydrolyzable organosilane compound and/or its partial hydrolyzed condensate is less than the above lower limit (0.1 part by mass), there is a risk of deterioration in curability and storage stability. On the other hand, when the above upper limit (40 parts by mass) is exceeded, not only is it disadvantageous in terms of cost, but also the elongation of the cured product may be lowered, and the durability may be lowered.
- condensation catalysts that have been commonly used as curing accelerators for condensation-curable liquid silicone adhesives (room-temperature-curing organopolysiloxane compositions) can be used.
- the amount of the curing catalyst is 0.001 to 20 parts by weight per 100 parts by weight of the linear diorganopolysiloxane having both molecular chain ends blocked with silicon-bonded hydroxyl groups and/or hydrolyzable silyl groups. , preferably 0.005 to 5 parts by mass, more preferably 0.01 to 2 parts by mass. If the amount of the curing catalyst is less than the above lower limit (0.001 parts by mass), the catalytic effect may not be obtained, and if the amount of the curing catalyst exceeds the above upper limit (20 parts by mass) In addition to being disadvantageous in terms of price, the durability of the composition may be lowered, or the adhesiveness may be lowered.
- the condensation-curing liquid silicone adhesive further contains, as component (F), a silane coupling agent (a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) that improves adhesive strength and acts as an adhesion imparting component.
- a silane coupling agent a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.
- a silane coupling agent known in the technical field is preferably used as the adhesion-imparting component.
- those having an alkoxy group or an alkenoxy group are preferable as the hydrolyzable group.
- alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, a vinyloxy group, an isopropenoxy group, and 1-ethyl-2-methyl Examples include alkenoxy groups such as vinyloxy groups.
- the monovalent hydrocarbon group substituted with a functional group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom includes an unsubstituted or substituted amino group, an unsubstituted or substituted Those having a monovalent hydrocarbon group of 1 to 20 carbon atoms having at least one imino group, mercapto group, epoxy group, (meth)acryloxy group, etc.
- ⁇ -acryloxypropyl group ⁇ -methacryloxypropyl group, ⁇ -(3,4-epoxycyclohexyl)ethyl group, ⁇ -glycidoxypropyl group, N- ⁇ (aminoethyl) ⁇ -aminopropyl group, ⁇ -aminopropyl group, the following formula and a ⁇ -mercaptopropyl group.
- the silane coupling agent may have an organic group bonded to a silicon atom other than the monovalent hydrocarbon group substituted with the above hydrolyzable group and functional group.
- a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable.
- alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, heptyl group, octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, alkenyl groups such as allyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; Among them, a methyl group and an ethyl group are preferable.
- silane coupling agents include ⁇ -acryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -glycidoxypropyl.
- Use of an amino group-containing silane coupling agent is particularly preferred.
- the silane coupling agents may be used singly or in combination of two or more.
- the amount of the silane coupling agent (F) to be blended is based on 100 parts by mass of a linear diorganopolysiloxane having both ends of the molecular chain blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight. If it is less than 0.05 parts by mass, sufficient adhesiveness cannot be obtained, and if it exceeds 20 parts by mass, the weather resistance and mechanical properties will be poor.
- the condensation-curing liquid silicone adhesive can contain optional components within a range that does not impair the purpose of the present invention.
- the optional components include inorganic fillers other than components (A) and (B), pigments, dyes, coloring agents such as fluorescent brightening agents; antibacterial agents; antifungal agents; silicone oil (non-functional organopolysiloxane). and other plasticizers.
- inorganic fillers other than the optional components (A) and (B) include dry silica (fumed silica, etc.), wet silica (precipitated silica, etc.), fine quartz powder, diatomaceous Soil powder, particulate alumina, magnesia powder, and fine powder inorganic fillers obtained by surface-treating these with silanes, silazanes, low-polymerization polysiloxanes, etc. (excluding components (A) and (B)) ) can be exemplified.
- the blending amount is 0 per 100 parts by mass of linear diorganopolysiloxane having both ends of the molecular chain blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. .1 to 800 parts by mass, more preferably 0.5 to 600 parts by mass.
- the condensation-curing liquid silicone adhesive is prepared by uniformly mixing the above-described components using a known mixer in a state where moisture is blocked (in a dry atmosphere or under reduced pressure) according to a conventional method. be able to.
- the resulting condensation-curable liquid silicone adhesive is cured, for example, by leaving it at room temperature (23°C ⁇ 15°C).
- room temperature 23°C ⁇ 15°C
- Known methods and conditions according to the type can be adopted, for example, leaving it in the atmosphere for several hours to several days (e.g., 6 hours to 7 days) under the conditions of 23 ° C./50% RH. It can be cured by
- the addition reaction curing type liquid silicone adhesive contains (G) a silicon-bonded vinyl Linear diorganopolysiloxane (base polymer) whose molecular chain ends are blocked with silyl groups having alkenyl groups such as groups, (H) at least two silicon-bonded hydrogen atoms (SiH groups) in the molecule and (I) a platinum group metal catalyst (hydrosilylation addition reaction catalyst), which is crosslinked by the addition reaction (hydrosilylation reaction) of the SiH group to the vinyl group to obtain a cured product.
- Liquid silicone adhesive is a silicon-bonded vinyl Linear diorganopolysiloxane (base polymer) whose molecular chain ends are blocked with silyl groups having alkenyl groups such as groups, (H) at least two silicon-bonded hydrogen atoms (SiH groups) in the molecule and (I) a platinum group metal catalyst (hydrosilylation addition reaction catalyst), which is crosslinked by the addition reaction (hydrosilylation reaction) of the SiH
- the alkenyl group-containing organopolysiloxane as the base polymer (main ingredient) is capped with a silyl group having an alkenyl group such as a vinyl group bonded to a silicon atom at the molecular chain ends (one or both ends of the molecular chain).
- alkenyl group examples include, for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like.
- a lower alkenyl group having about 4 groups and the like can be mentioned.
- the alkenyl group-containing organopolysiloxane as the base polymer (main agent) has alkenyl groups in the side chains of the molecular chain, provided that it has alkenyl groups bonded to silicon atoms at one or both ends of the molecular chain. may be
- the silicon-bonded organic group other than the silicon-bonded alkenyl group is not particularly limited as long as it does not have an aliphatic unsaturated bond.
- Examples include 1 to 12, preferably 1 to 10, monovalent hydrocarbon groups excluding aliphatic unsaturated bonds.
- Examples of the unsubstituted or substituted monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as groups, tolyl groups, xylyl groups, and naphthyl groups; aralkyl groups such as benzyl groups and phenethyl groups; Examples thereof include substituted halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, and 3,3,3-trifluoropropyl group, preferably alkyl groups and aryl groups, and more preferably methyl groups. , is a phenyl group.
- alkenyl group-containing organopolysiloxane examples include dimethylpolysiloxane blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane/methylvinylsiloxane copolymer blocked at both ends with dimethylvinylsiloxy groups, and dimethylsiloxane/diphenyl at both ends blocked with dimethylvinylsiloxy groups.
- Siloxane copolymer both ends dimethylvinylsiloxy group-blocked dimethylsiloxane/methylvinylsiloxane/diphenylsiloxane copolymer, both ends dimethylvinylsiloxy group-blocked methyltrifluoropropylpolysiloxane, both ends dimethylvinylsiloxy group-blocked dimethylsiloxane/methyl Trifluoropropylsiloxane copolymer, both ends dimethylvinylsiloxy group-blocked dimethylsiloxane/methyltrifluoropropylsiloxane/methylvinylsiloxane copolymer, both ends methyldivinylsiloxy group-blocked dimethylpolysiloxane, both ends methyldivinylsiloxy group-blocked dimethyl Siloxane/methylvinylsiloxane copolymer, dimethylsiloxane/diphenylsiloxane cop
- the viscosity of the alkenyl group-containing organopolysiloxane as the base polymer (main agent) at 23°C is preferably 100 to 500,000 mPa ⁇ s, more preferably 700 to 100,000 mPa ⁇ s.
- the alkenyl group-containing organopolysiloxane as the base polymer (main agent) may be used alone or in combination of two or more.
- the organohydrogenpolysiloxane as a cross-linking agent has an average of at least 2, preferably at least 3, more preferably an upper limit of 500, still more preferably an upper limit of 200, Particularly preferred are those having up to 100 silicon-bonded hydrogen atoms (SiH groups) and preferably having no aliphatic unsaturated bonds in the molecule.
- the silicon-bonded organic group other than the silicon-bonded hydrogen atom is not particularly limited, but is, for example, an unsubstituted or substituted group having usually 1 to 10 carbon atoms, preferably 1 to 6 monovalent hydrocarbon groups, and the like.
- Specific examples thereof include the same silicon-bonded organic groups other than the silicon-bonded alkenyl groups exemplified in the description of the alkenyl-containing organopolysiloxane, and alkenyl groups such as vinyl groups and allyl groups.
- an unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond such as an alkyl group or an aryl group, more preferably a methyl group, a phenyl group or the like.
- the number of silicon atoms in the molecule is 2 to 300, particularly 3 to 150, especially 4 to 100, and liquid at room temperature is preferably used.
- the hydrogen atoms bonded to the silicon atoms may be located either at the molecular chain terminal, in the middle (non-terminal) of the molecular chain, or at both.
- the molecular structure of the organohydrogenpolysiloxane may be linear, cyclic, branched, or three-dimensional network.
- the degree of polymerization (or the repeating number of diorganosiloxane units constituting the main chain, which is a measure of the number of silicon atoms in the molecule) is analyzed by gel permeation chromatography (GPC) using, for example, toluene as a developing solvent. It can be obtained as a polystyrene-equivalent number-average polymerization degree (or number-average molecular weight) or the like.
- organohydrogenpolysiloxanes examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrogendimethylsiloxy)methylsilane, tris(hydrogen dimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane/methylhydrogensiloxane Copolymer, dimethylpolysiloxane blocked at both ends by dimethylhydrogensiloxy groups, dimethylsiloxane/methylhydrogensiloxane copolymer blocked at both ends by dimethylhydrogensiloxy groups, copolymer of methylhydrogensiloxane/diphenyl
- the organohydrogenpolysiloxane may be used singly or in combination of two or more.
- the amount of organohydrogenpolysiloxane to be added is 0.01 to 3 mol, preferably 0, of silicon-bonded hydrogen atoms (SiH groups) per 1 mol of silicon-bonded alkenyl groups in the alkenyl-containing organopolysiloxane. 0.05 to 2.5 mol, more preferably 0.2 to 2 mol.
- the platinum group metal catalyst (hydrosilylation addition reaction catalyst) promotes the addition reaction between the silicon-bonded alkenyl groups in the alkenyl-containing organopolysiloxane and the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane. It is used as a catalyst for A known platinum group metal catalyst can be used. Specific examples thereof include platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, and platinum-based catalysts such as complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like.
- the amount of the platinum group metal catalyst may be an effective amount, and can be appropriately increased or decreased depending on the desired curing rate. In terms of mass, it is usually in the range of 0.1 to 1,000 ppm, preferably 1 to 300 ppm. If the blending amount is too large, the heat resistance of the resulting cured product may be lowered.
- the addition reaction curing type liquid silicone adhesive further improves the adhesive strength and has an action as an adhesion-imparting component (J) a silane coupling agent (a functional group having a heteroatom such as an oxygen atom or a sulfur atom). It is preferable to add a hydrolyzable silane compound having a monovalent hydrocarbon group substituted with in the molecule, a so-called carbon functional silane compound.
- a silane coupling agent known in the technical field is preferably used as the adhesion-imparting component. Specifically, the same silane coupling agents as exemplified for the component (F) described above can be exemplified.
- the blending amount is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the alkenyl group-containing organopolysiloxane (base polymer). parts, particularly preferably 0.5 to 10 parts by mass. If it is less than 0.05 parts by mass, sufficient adhesion may not be obtained, and if it exceeds 20 parts by mass, the weather resistance and mechanical properties may be poor.
- optional components can be added to the addition reaction curing type liquid silicone adhesive within a range that does not impair the purpose of the present invention.
- the optional components include, for example, reaction inhibitors, and inorganic fillers similar to those exemplified in the condensation-curable liquid silicone-based adhesive described above (however, component (A), particles that generate heat when exposed to microwaves, and (B), Hydroxy compounds whose component decomposition temperature is 180 to 600 ° C), organopolysiloxanes that do not contain silicon-bonded hydrogen atoms (SiH groups) and silicon-bonded alkenyl groups (so-called non-functional silicone oils), heat-resistant additives agents, flame retardants, thixotropic agents, pigments, dyes, and the like.
- the addition reaction-curing liquid silicone adhesive can be prepared by uniformly mixing the above components using a known mixer according to a conventional method.
- the curing conditions for the addition reaction curing type liquid silicone adhesive are 23 to 150° C., particularly 23 to 100° C., and 10 minutes to 8 hours, particularly 30 minutes to 5 hours.
- the joining member is a cured product obtained by curing a curable liquid silicone adhesive containing particles that generate heat by microwaves and a hydroxide compound having a decomposition temperature of 180 to 600°C.
- the members are preferably the same or different members selected from resin members and metal members, and more preferably at least one (one) of the plurality of joined members is an organic resin member.
- Such a combination of members includes, for example, a combination of the same or different organic resin members, a combination of a metal member and an organic resin member, and the like.
- organic resins that make up the organic resin member include PBT (polybutylene terephthalate resin), PPS (polyphenylene sulfide resin), polyamide resins such as PA66 (nylon 66) and PA6 (nylon 6), and PC (polycarbonate resin).
- Examples of metals forming the metal member include aluminum, iron, SUS, and copper. It is desirable that the above organic resin or metal constituting the organic resin member or the metal member has a heat resistance temperature of 160° C. or higher.
- a curable liquid silicone adhesive containing particles that generate heat by microwaves and a hydroxide compound with a decomposition temperature of 180 to 600° C. is applied manually or mechanically onto the surface of a member made of organic resin or metal on one side. It is applied to the shape of a joint (for example, a gasket), and the other member made of organic resin or metal is pasted and joined, and then cured. Then fix with bolts, etc., if necessary.
- the curable liquid silicone adhesive of the present invention is a condensation-curable liquid silicone adhesive, it cures at room temperature by moisture in the air. . Humidification is effective in accelerating hardening.
- the curable liquid silicone adhesive of the present invention is an addition reaction curable liquid silicone adhesive, it cures by the addition reaction at a temperature of 23 to 150° C. Therefore, after combining a plurality of members, it can be left alone or heated. Hardening proceeds.
- Examples of the bonding member include automobile parts such as engines, transmissions, ECUs and PCUs, and electric/electronic parts such as smartphones, tablets, liquid crystals, and batteries. preferable.
- the joining member maintains the joining state of the member at a usage environment temperature of 150°C or less, preferably room temperature to 120°C.
- the joining member is preferably an easily dismantled joining member that is joined with a certain degree of adhesive strength during normal use, and whose adhesive strength is reduced to the extent that the members can be separated after heating.
- the initial shear adhesive strength of the bonding member is preferably 1.2 MPa or more, particularly 1.5 MPa or more, and the shear adhesive strength of the bonding member after microwave irradiation is 1 MPa or less. preferable.
- This shear adhesive strength is a value measured according to the method specified in JIS K6850.
- the composition of the curable liquid silicone adhesive can be adjusted to the specific range described above.
- a cured product obtained by curing a curable liquid silicone adhesive, which is an adhesive member of the joining member, is irradiated with microwaves, and then cooled to room temperature.
- the members peel off naturally, or apply force to them by hand, or use an instrument such as a scraper to separate multiple (especially two) members such as organic resin and / or metal
- the joining member can be dismantled by peeling. Also, the dismantled members can be recycled.
- the frequency, output, and duration of the microwaves to be irradiated are such that the adhesive strength is reduced to the extent that the members can be separated after irradiation.
- the frequency can be selected in the range of 300 MHz or more and 300 GHz or less, and the output can be selected in the range of 300 W or more and 5,000 W or less.
- the microwave irradiation time is not particularly limited, but is 30 minutes or less, preferably 15 minutes or less, more preferably 5 minutes or less.
- composition examples, composition comparative examples, examples and comparative examples are shown to specifically describe the present invention, but the present invention is not limited to the following examples.
- the room temperature is 23° C.
- the viscosity is the value at 23° C. measured by a rotational viscometer
- the average particle size is the cumulative weight average value using a particle size distribution measuring device based on the laser light diffraction method. Values determined as D50 (or median diameter) are shown.
- the dielectric constant shows the value at 3 GHz.
- composition Example 1 100 parts by mass of dimethylpolysiloxane having a viscosity of 30,000 mPa s, an average particle size of 8 ⁇ m, and an untreated surface of acetylene black powder (dielectric constant: 37), both molecular chain ends of which are blocked with trimethoxysilyl groups.
- a composition 1 was obtained by uniformly mixing 0.5 parts by mass of the compound and 0.1 parts by mass of dioctyltin dineodecanoate.
- composition Example 2 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa s and having both ends of the molecular chain blocked with hydroxyl groups, 12 parts by mass of acetylene black powder having an average particle size of 8 ⁇ m and an untreated surface (dielectric constant: 37) (5.0% by mass of the total composition), 120 parts by mass of untreated magnesium hydroxide having an average particle size of 1 ⁇ m (50.2% by mass of the total composition), vinyl 6 parts by mass of trimethoxysilane, 0.5 parts by mass of ⁇ -aminopropyltriethoxysilane, and 0.5 parts by mass of the compound obtained by the dehydrochlorination reaction of xylylenediamine represented by the above formula (1) and 3-chloropropyltrimethoxysilane. 5 parts by mass and 0.1 part by mass of dioctyltin dineodecanoate were uniformly mixed to obtain composition 2.
- composition Example 3 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa s, an average particle size of 0.3 ⁇ m, and a surface treated with alumina and silica (amount of surface treatment: 5 % by mass) titanium dioxide (dielectric constant: 96) 20 parts by mass (content of 8.1% by mass in the entire composition), 120 parts by mass of aluminum hydroxide having an average particle diameter of 10 ⁇ m and an untreated surface (composition 5 parts by mass of phenyltriisopropenoxysilane, 0.5 parts by mass of ⁇ -aminopropyltriethoxysilane, xylylenediamine represented by the above formula (1) and 3-
- a composition 3 was obtained by uniformly mixing 0.5 parts by mass of a compound obtained by a dehydrochlorination reaction of chloropropyltrimethoxysilane and 0.7 parts by mass of tetramethylguanidylpropyltrimethoxysilane
- composition Comparative Example 1 100 parts by mass of dimethylpolysiloxane having a viscosity of 30,000 mPa ⁇ s and having both ends of the molecular chain blocked with trimethoxysilyl groups, 12 parts by mass of fumed silica, 4 parts by mass of vinyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane 0.5 parts by mass, 0.5 parts by mass of the compound obtained by the dehydrochlorination reaction of xylylenediamine represented by the above formula (1) and 3-chloropropyltrimethoxysilane, and 0.5 part by mass of dioctyltin dineodecanoate.
- a composition 4 was obtained by uniformly mixing 1 part by mass.
- composition Comparative Example 2 100 parts by mass of dimethylpolysiloxane having a viscosity of 30,000 mPa ⁇ s and 120 parts by mass of aluminum hydroxide having an average particle size of 10 ⁇ m and an untreated surface (composition 5 parts by mass of fumed silica, 4 parts by mass of vinyltrimethoxysilane, 0.5 parts by mass of ⁇ -aminopropyltriethoxysilane, xylylene represented by the above formula (1)
- a composition 5 was obtained by uniformly mixing 0.5 parts by mass of a compound obtained by the dehydrochlorination reaction of amine and 3-chloropropyltrimethoxysilane and 0.1 parts by mass of dioctyltin dineodecanoate.
- composition Comparative Example 3 100 parts by mass of dimethylpolysiloxane having a viscosity of 30,000 mPa s, an average particle size of 8 ⁇ m, and an untreated surface of acetylene black powder (dielectric constant: 37), both molecular chain ends of which are blocked with trimethoxysilyl groups.
- composition 6 0.3 parts by mass (content of 0.1% by mass in the entire composition), 120 parts by mass of aluminum hydroxide having an average particle diameter of 10 ⁇ m and an untreated surface (content of 53.2 parts by mass in the entire composition) % by mass), 4 parts by mass of vinyltrimethoxysilane, 0.5 parts by mass of ⁇ -aminopropyltriethoxysilane, obtained by the dehydrochlorination reaction of xylylenediamine represented by the above formula (1) and 3-chloropropyltrimethoxysilane. 0.5 parts by mass of the obtained compound and 0.1 parts by mass of dioctyltin dineodecanoate were uniformly mixed to obtain composition 6.
- Adhesive strength (initial) was measured according to the method specified in JIS K6850.
- Adhesion (after microwave irradiation)
- the bonding member prepared above was irradiated with a frequency of 2.4 GHz and an output of 1,000 W for the time shown in the table, and then cooled to room temperature. After) was measured by the same method as (1).
- a composition in which the substrates were decomposed after microwave irradiation and before the measurement of the shear adhesive strength was regarded as delamination.
- the cured product of the curable liquid silicone-based adhesive used in the method for dismantling a joint member of the present invention has a reduced adhesive strength due to the decomposition of the hydroxide compound by irradiation with microwaves. .
- Comparative Examples 1 and 2 no heat-generating particles exist even when irradiated with microwaves, so dismantling properties cannot be obtained.
- the adhesive force of the cured adhesive silicone rubber hardly changes even when irradiated with microwaves, and the heat resistance (adhesiveness) is maintained. could not.
- Comparative Example 3 there are particles that generate heat by microwaves, but since the content is less than the specified amount, a sufficient heat generation effect cannot be obtained, the adhesive force is insufficiently reduced, and the dismantling property is poor. I could't.
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Abstract
Description
[1]
マイクロ波により発熱する粒子と分解温度が180~600℃である水酸化化合物を含有し、該マイクロ波により発熱する粒子の含有量が0.5~50質量%である硬化性液状シリコーン系接着剤を硬化させてなる硬化物で複数の部材同士が接合された接合部材について、該硬化物にマイクロ波を照射することにより、前記複数の部材同士を分離して接合部材を解体する工程を含む接合部材の解体方法。
[2]
硬化性液状シリコーン系接着剤が、縮合硬化型液状シリコーン系接着剤又は付加反応硬化型液状シリコーン系接着剤である[1]に記載の接合部材の解体方法。
[3]
マイクロ波により発熱する粒子が、炭素、酸化鉄、酸化チタン、フェライト及び炭化ケイ素から選ばれる少なくとも1種の粒子である[1]又は[2]に記載の接合部材の解体方法。
[4]
分解温度が180~600℃である水酸化化合物が、水酸化アルミニウム、水酸化マグネシウム及び水酸化酸化アルミニウム(べーマイト)から選ばれる少なくとも1種である[1]~[3]のいずれかに記載の接合部材の解体方法。
[5]
マイクロ波の波長が、300MHz以上300GHz以下である[1]~[4]のいずれかに記載の接合部材の解体方法。
[6]
分解温度が180~600℃である水酸化化合物の含有量が、硬化性液状シリコーン系接着剤全体の35~65質量%である[1]~[5]のいずれかに記載の接合部材の解体方法。
[7]
上記接合部材の解体が人手又はスクレーパーにより前記複数の部材から硬化性液状シリコーン系接着剤の硬化物を剥離する工程を含むものである[1]~[6]のいずれかに記載の接合部材の解体方法。
[8]
接合部材が自動車部品又は電気・電子部品である[1]~[7]のいずれかに記載の接合部材の解体方法。
[9]
[1]~[8]のいずれかに記載の接合部材の解体方法に用いられる接合部材。
[10]
[1]~[8]のいずれかに記載の接合部材の解体方法に用いられる下記(A)~(F)成分を含有する易解体性の縮合硬化型液状シリコーン系接着剤。
(A)マイクロ波により発熱する粒子:接着剤全体の0.5~50質量%、
(B)分解温度が180~600℃である水酸化化合物:接着剤全体の35~65質量%、
(C)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン:100質量部、
(D)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物:0.1~40質量部、
(E)硬化触媒:0.001~20質量部、及び
(F)シランカップリング剤:0.05~20質量部。
[11]
[1]~[8]のいずれかに記載の接合部材の解体方法に用いられる下記(A)、(B)及び(G)~(I)成分を含有する易解体性の付加反応硬化型液状シリコーン系接着剤。
(A)マイクロ波により発熱する粒子:接着剤全体の0.5~50質量%、
(B)分解温度が180~600℃である水酸化化合物:接着剤全体の35~65質量%、
(G)ケイ素原子に結合したアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン:100質量部、
(H)ケイ素原子に結合した水素原子を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン:(G)成分中のケイ素原子に結合したアルケニル基1モルに対してケイ素原子結合水素原子が0.01~3モルとなる量、及び
(I)白金族金属触媒:(G)成分と(H)成分の合計量に対して白金族金属原子の質量換算で0.01~1,000ppm。
なお、本発明において、解体する部材の「耐熱温度」とは、当該部材を特定の温度下に1分間静置した際に、該部材が熱分解又は軟化を生じない温度の上限を意味する。
本発明の接合部材の解体方法は、マイクロ波により発熱する粒子と分解温度が180~600℃である水酸化化合物を含有し、該マイクロ波により発熱する粒子の含有量が0.5~50質量%である硬化性液状シリコーン系接着剤を硬化させてなる硬化物で複数の部材同士が接合された接合部材について、該硬化物にマイクロ波を照射することにより前記複数の部材、特に有機樹脂製及び/又は金属製等の部材同士を分離して接合部材を解体する工程を含むものである。
本発明に使用される硬化性液状シリコーン系接着剤は、硬化して複数の部材、特に有機樹脂製及び/又は金属製等の部材同士を接合する接着部材となるもので、マイクロ波により発熱する粒子(A)と分解温度が180~600℃である水酸化化合物(B)を含有し、該マイクロ波により発熱する粒子(A)の含有量が0.5~50質量%であり、主鎖がシロキサン結合からなる高分子をベースポリマーに使用した接着剤であり、硬化タイプは、縮合硬化型、付加反応硬化型が好ましい。
本発明に使用されるマイクロ波により発熱する粒子(A)は、マイクロ波の照射により粒子が発熱することにより、硬化性液状シリコーン系接着剤中に配合された水酸化化合物(特には金属水酸化物又は酸化金属の水酸化物)が分解し、該水酸化化合物の分解に伴って水が発生することにより接着剤が発泡して接着力の低下が起き、短時間かつ少ない消費エネルギーで容易に接合部材を解体することができるものである。
分解温度が180~600℃である水酸化化合物(B)は、通常、金属の水酸化物又は酸化金属の水酸化物であることが好ましく、分解温度が180℃付近である水酸化アルミニウム、分解温度が300℃付近である水酸化マグネシウム、分解温度が500℃付近である水酸化酸化アルミニウム(べーマイト)を挙げることができる。
なお、硬化性液状シリコーン系接着剤におけるマイクロ波により発熱する粒子(A)と、水酸化化合物(B)の合計含有量は36~85質量%が好ましく、40~75質量%がより好ましく、45~65質量%であることが更に好ましい。また、マイクロ波により発熱する粒子(A)と水酸化化合物(B)との質量比は1:0.8~1:50が好ましく、1:1~1:30がより好ましく、1:2~1:20が更に好ましい。
縮合硬化型液状シリコーン系接着剤は、上述した(A)マイクロ波により発熱する粒子と(B)分解温度が180~600℃である水酸化化合物以外に、(C)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン(ベースポリマー)、(D)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物(架橋剤)、(E)硬化触媒、及び(F)シランカップリング剤(接着性付与剤)を含み、室温において大気中の水分(湿気)による加水分解・縮合反応を利用して硬化物を得る液状シリコーン系接着剤である。
加水分解性シリル基として末端にアルコキシシリル基又はアルコキシ置換アルコキシシリル基を有する場合は、分子鎖の両末端に、ケイ素原子に結合するアルコキシ基(即ち、アルコキシシリル基)又はケイ素原子に結合するアルコキシ置換アルコキシ基(即ち、アルコキシアルコキシシリル基)を、2つ又は3つずつ有する(即ち、ジアルコキシオルガノシリル基又はビス(アルコキシアルコキシ)オルガノシリル基や、トリアルコキシシリル基又はトリス(アルコキシアルコキシ)シリル基として存在する)のがよい。
アルコキシ置換アルコキシ基としては、炭素原子数2~10、特に炭素原子数2~4のアルコキシ置換アルコキシ基が好ましく、例えば、メトキシエトキシ基、エトキシエトキシ基、メトキシプロポキシ基等が挙げられる。
シランカップリング剤は、1種単独でも2種以上を組み合わせて使用してもよい。
付加反応硬化型液状シリコーン系接着剤は、上述した(A)マイクロ波により発熱する粒子と(B)分解温度が180~600℃である水酸化化合物以外に、(G)ケイ素原子に結合したビニル基等のアルケニル基を有するシリル基で分子鎖末端が封鎖された直鎖状ジオルガノポリシロキサン(ベースポリマー)、(H)ケイ素原子に結合した水素原子(SiH基)を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン(架橋剤)、及び(I)白金族金属触媒(ヒドロシリル化付加反応触媒)を含み、SiH基のビニル基への付加反応(ヒドロシリル化反応)により架橋し硬化物を得る液状シリコーン系接着剤である。
また、付加反応硬化型液状シリコーン系接着剤の硬化条件としては、23~150℃、特に23~100℃にて10分~8時間、特に30分~5時間とすることができる。
本発明の接合部材の解体方法において、接合部材は、マイクロ波により発熱する粒子と分解温度が180~600℃である水酸化化合物を含有する硬化性液状シリコーン系接着剤を硬化させてなる硬化物(接着性シリコーンゴム硬化物からなる接着部材)によって同一又は異種の複数(特には2個)の部材同士が接合された接合部材であって、該接合部材において、接合された各部材は、有機樹脂製部材及び金属製部材から選ばれる同一又は異種のものであることが好ましく、接合された複数の部材のうち少なくとも1個(一方)が有機樹脂製部材であることがより好ましい。このような部材の組合せとしては、例えば、同一又は異種の有機樹脂製の部材同士の組合せ、金属製部材と有機樹脂製部材の組合せなどが挙げられる。有機樹脂製部材を構成する有機樹脂としては、PBT(ポリブチレンテレフタレート樹脂)、PPS(ポリフェニレンサルファイド樹脂)、PA66(ナイロン66)、PA6(ナイロン6)等のポリアミド樹脂、PC(ポリカーボネート樹脂)などが挙げられ、金属製部材を構成する金属としては、例えば、アルミニウム、鉄、SUS、銅などが挙げられる。なお、有機樹脂製部材又は金属製部材を構成する上記の有機樹脂又は金属は、それぞれ耐熱温度が160℃以上であることが望ましい。
マイクロ波により発熱する粒子と分解温度が180~600℃である水酸化化合物を含有する硬化性液状シリコーン系接着剤を、手又は機械吐出で片側の有機樹脂製又は金属製等の部材の表面に接合箇所(例えばガスケット等)の形状に塗布し、もう一方の有機樹脂製又は金属製等の部材を貼り合わせて接合し、硬化させる。その後必要に応じてボルトなどで固定する。本発明の硬化性液状シリコーン系接着剤が縮合硬化型液状シリコーン系接着剤の場合、室温において空気中の湿分によって硬化するので、複数の部材を合体後、放置しておけば硬化が進行する。硬化を促進させたい場合には加湿することが有効である。また、本発明の硬化性液状シリコーン系接着剤が付加反応硬化型液状シリコーン系接着剤の場合、23~150℃の温度において付加反応により硬化するので、複数の部材を合体後、放置又は加熱すれば硬化が進行する。
本発明の接合部材の解体方法は、接合部材の接着部材である硬化性液状シリコーン系接着剤を硬化させてなる硬化物(接着性シリコーンゴム硬化物)にマイクロ波を照射後、室温まで冷却し、部材同士が自然に剥離するか、あるいはこれに手で力を加えるか、又はスクレーパーなどの器具を使用して有機樹脂製及び/又は金属製等の複数(特には2個)の部材同士を剥離させることにより接合部材を解体することができる。また、解体した部材はリサイクルすることが可能である。
(1)マイクロ波の照射により、(A)成分の粒子が発熱する。
(2)(A)成分の粒子の発熱により、(B)成分の水酸化化合物が加熱され、該(B)成分の水酸化化合物が分解して水を発生する。
(3)発生した水が、(A)成分の粒子の発熱及びマイクロ波の照射により加熱されて気化することにより発泡する。
(4)硬化物内におけるこの発泡により接合部材の接着力が低下する。
[組成物実施例1]
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン100質量部、平均粒子径が8μmであり、表面が未処理のアセチレンブラック粉末(誘電率:37)12質量部(組成物全体中の含有量5.1質量%)、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム120質量部(組成物全体中の含有量50.6質量%)、ビニルトリメトキシシラン4質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、下記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びジオクチルスズジネオデカノエート0.1質量部を均一に混ぜ、組成物1を得た。
分子鎖両末端が水酸基で封鎖され、粘度が20,000mPa・sのジメチルポリシロキサン100質量部、平均粒子径が8μmであり、表面が未処理のアセチレンブラック粉末(誘電率:37)12質量部(組成物全体中の含有量5.0質量%)、平均粒子径が1μmであり、表面が未処理の水酸化マグネシウム120質量部(組成物全体中の含有量50.2質量%)、ビニルトリメトキシシラン6質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、上記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びジオクチルスズジネオデカノエート0.1質量部を均一に混ぜ、組成物2を得た。
分子鎖両末端が水酸基で封鎖され、粘度が20,000mPa・sのジメチルポリシロキサン100質量部、平均粒子径が0.3μmであり、表面がアルミナとシリカで処理された(表面処理量:5質量%)二酸化チタン(誘電率:96)20質量部(組成物全体中の含有量8.1質量%)、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム120質量部(組成物全体中の含有量48.6質量%)、フェニルトリイソプロペノキシシラン5質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、上記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びテトラメチルグアニジルプロピルトリメトキシシラン0.7質量部を均一に混ぜ、組成物3を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン100質量部、煙霧質シリカ12質量部、ビニルトリメトキシシラン4質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、上記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びジオクチルスズジネオデカノエート0.1質量部を均一に混ぜ、組成物4を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン100質量部、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム120質量部(組成物全体中の含有量52.2質量%)、煙霧質シリカ5質量部、ビニルトリメトキシシラン4質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、上記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びジオクチルスズジネオデカノエート0.1質量部を均一に混ぜ、組成物5を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン100質量部、平均粒子径が8μmであり、表面が未処理のアセチレンブラック粉末(誘電率:37)0.3質量部(組成物全体中の含有量0.1質量%)、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム120質量部(組成物全体中の含有量53.2質量%)、ビニルトリメトキシシラン4質量部、γ-アミノプロピルトリエトキシシラン0.5質量部、上記式(1)で示されるキシリレンジアミンと3-クロロプロピルトリメトキシシランの脱塩酸反応により得られた化合物0.5質量部、及びジオクチルスズジネオデカノエート0.1質量部を均一に混ぜ、組成物6を得た。
基材として幅25mm、長さ100mmのPBT(ポリブチレンテレフタレート樹脂、耐熱温度:150℃以上)製基材を2枚使用し、硬化性液状シリコーン系接着剤として上記組成物1~6のいずれかを使用し、接着厚みが0.5mm、接着面積が2.5cm2になるように2枚のPBT基材同士を貼り合わせ、23℃/50%RHにて7日間養生することによって、硬化性液状シリコーン系接着剤の硬化物(接着性シリコーンゴム硬化物)で2枚のPBT基材同士が接合された接合部材を作製した。
[実施例1~3、比較例1~3]
上記で作製した接合部材を用いて、下記に示す評価方法により接着力(解体性)の評価を行った。これらの結果を表1に示す。
上記で作製した接合部材を用いて、せん断接着力(初期)をJIS K6850に規定する方法に準じて測定した。
上記で作製した接合部材を、周波数2.4GHz、出力1,000Wで表中記載の時間照射後、室温になるまで冷却し、PBT部材に対する接着性シリコーンゴム硬化物のせん断接着力(マイクロ波照射後)を(1)と同様の方法により測定した。なお、マイクロ波照射後、せん断接着力測定前に基材同士が分解した組成物は剥離とした。
一方、比較例1、2ではマイクロ波を照射しても発熱粒子が存在しないため、解体性は得られない。即ち、マイクロ波を照射しても接着性シリコーンゴム硬化物(接着部材)の接着力はほとんど変化しておらず、耐熱性(接着性)を維持しているため、接合部材を解体することはできなかった。
また、比較例3ではマイクロ波により発熱する粒子が存在するが、含有量が規定量以下で少ないため、十分な発熱効果が得られず、接着力の低下が不十分であり、解体性は得られなかった。
Claims (11)
- マイクロ波により発熱する粒子と分解温度が180~600℃である水酸化化合物を含有し、該マイクロ波により発熱する粒子の含有量が0.5~50質量%である硬化性液状シリコーン系接着剤を硬化させてなる硬化物で複数の部材同士が接合された接合部材について、該硬化物にマイクロ波を照射することにより、前記複数の部材同士を分離して接合部材を解体する工程を含む接合部材の解体方法。
- 硬化性液状シリコーン系接着剤が、縮合硬化型液状シリコーン系接着剤又は付加反応硬化型液状シリコーン系接着剤である請求項1に記載の接合部材の解体方法。
- マイクロ波により発熱する粒子が、炭素、酸化鉄、酸化チタン、フェライト及び炭化ケイ素から選ばれる少なくとも1種の粒子である請求項1又は2に記載の接合部材の解体方法。
- 分解温度が180~600℃である水酸化化合物が、水酸化アルミニウム、水酸化マグネシウム及び水酸化酸化アルミニウム(べーマイト)から選ばれる少なくとも1種である請求項1~3のいずれか1項に記載の接合部材の解体方法。
- マイクロ波の波長が、300MHz以上300GHz以下である請求項1~4のいずれか1項に記載の接合部材の解体方法。
- 分解温度が180~600℃である水酸化化合物の含有量が、硬化性液状シリコーン系接着剤全体の35~65質量%である請求項1~5のいずれか1項に記載の接合部材の解体方法。
- 上記接合部材の解体が人手又はスクレーパーにより前記複数の部材から硬化性液状シリコーン系接着剤の硬化物を剥離する工程を含むものである請求項1~6のいずれか1項に記載の接合部材の解体方法。
- 接合部材が自動車部品又は電気・電子部品である請求項1~7のいずれか1項に記載の接合部材の解体方法。
- 請求項1~8のいずれか1項に記載の接合部材の解体方法に用いられる接合部材。
- 請求項1~8のいずれか1項に記載の接合部材の解体方法に用いられる下記(A)~(F)成分を含有する易解体性の縮合硬化型液状シリコーン系接着剤。
(A)マイクロ波により発熱する粒子:接着剤全体の0.5~50質量%、
(B)分解温度が180~600℃である水酸化化合物:接着剤全体の35~65質量%、
(C)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン:100質量部、
(D)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物:0.1~40質量部、
(E)硬化触媒:0.001~20質量部、及び
(F)シランカップリング剤:0.05~20質量部。 - 請求項1~8のいずれか1項に記載の接合部材の解体方法に用いられる下記(A)、(B)及び(G)~(I)成分を含有する易解体性の付加反応硬化型液状シリコーン系接着剤。
(A)マイクロ波により発熱する粒子:接着剤全体の0.5~50質量%、
(B)分解温度が180~600℃である水酸化化合物:接着剤全体の35~65質量%、
(G)ケイ素原子に結合したアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン:100質量部、
(H)ケイ素原子に結合した水素原子を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン:(G)成分中のケイ素原子に結合したアルケニル基1モルに対してケイ素原子結合水素原子が0.01~3モルとなる量、及び
(I)白金族金属触媒:(G)成分と(H)成分の合計量に対して白金族金属原子の質量換算で0.01~1,000ppm。
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