JP6872944B2 - 低温加熱硬化型構造用接着剤組成物 - Google Patents
低温加熱硬化型構造用接着剤組成物 Download PDFInfo
- Publication number
- JP6872944B2 JP6872944B2 JP2017060693A JP2017060693A JP6872944B2 JP 6872944 B2 JP6872944 B2 JP 6872944B2 JP 2017060693 A JP2017060693 A JP 2017060693A JP 2017060693 A JP2017060693 A JP 2017060693A JP 6872944 B2 JP6872944 B2 JP 6872944B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- structural adhesive
- low
- temperature
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims description 72
- 230000001070 adhesive effect Effects 0.000 title claims description 72
- 239000000203 mixture Substances 0.000 title claims description 45
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 238000013007 heat curing Methods 0.000 claims description 5
- 239000003230 hygroscopic agent Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- -1 alicyclic diamine Chemical class 0.000 description 16
- 230000007547 defect Effects 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000013035 low temperature curing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- IJJNTMLAAKKCML-UHFFFAOYSA-N tribenzyl borate Chemical compound C=1C=CC=CC=1COB(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 IJJNTMLAAKKCML-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- KDQYHGMMZKMQAA-UHFFFAOYSA-N trihexyl borate Chemical compound CCCCCCOB(OCCCCCC)OCCCCCC KDQYHGMMZKMQAA-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- GZKLCETYSGSMRA-UHFFFAOYSA-N trioctadecyl borate Chemical compound CCCCCCCCCCCCCCCCCCOB(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC GZKLCETYSGSMRA-UHFFFAOYSA-N 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/188—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using encapsulated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D65/00—Designing, manufacturing, e.g. assembling, facilitating disassembly, or structurally modifying motor vehicles or trailers, not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D65/00—Designing, manufacturing, e.g. assembling, facilitating disassembly, or structurally modifying motor vehicles or trailers, not otherwise provided for
- B62D65/02—Joining sub-units or components to, or positioning sub-units or components with respect to, body shell or other sub-units or components
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
-
- 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
- C09J2463/00—Presence of epoxy resin
Description
また、接着剤の塗布工程では、接着性及びシール性を考慮して、溶接工程の挟圧によって接合端部と被接合部との隙間から接着剤が若干はみ出すように塗布要領が設定されている。塗布された加熱硬化型接着剤は、乾燥炉の熱を利用して硬化されているため、乾燥炉移動中において常温(例えば20℃)から硬化温度(例えば150℃)まで昇温される期間、所謂接着中期において、接着剤の粘度が一旦低下する物性を有しているため、接着剤のはみ出し部は、接合端部と被接合部との重ね合わせ部分から離隔するように外側へ流動し、このはみ出し部の移動に起因して溝欠陥が発生するおそれがあった。溝欠陥が発生すると電着塗装を破断して錆が発生するおそれがあるため、溝欠陥を生じない接着剤が求められている。これを実現する接着剤の条件として、特許文献2では温間中の複素粘度の最低値を200Pa・s以下に設定することを開示している。
B(OR1)(OR2)(OR3) ・・・(1)
(但し、R1〜R3は水素原子又は炭素数が20個以下のアルキル基或はアリール基を表す。R1〜R3は同一であっても異なってもよい。)具体的に例示すれば下記のものが挙げられる。即ち、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル、ホウ酸トリヘキシル、ホウ酸トリオクチル、ホウ酸トリステアリル、ホウ酸トリフェニル、ホウ酸トリトリル、ホウ酸トリキシリル、ホウ酸トリベンジル等である。これらのホウ酸エステルより1種類のもののみを用いても、2種類以上のものを組合せ用いてもよい。ホウ酸エステル化合物のアルキル基及び/又はアリール基の炭素数は20個を越えるとホウ酸エステル化合物中のホウ素原子の含有率が低下し、ホウ酸エステル化合物の有効性が著しく低下する。又、ホウ酸エステル化合物自体も固形化、高融点化し取扱い性が悪くなる。好ましい炭素原子数は1乃至12個であり、更に好ましくは1乃至8個である。
また、前記動的粘弾性測定におけるオープン放置の条件としては、例えば、接着剤を40℃、相対湿度85%にて4日間オープン放置する条件が挙げられる。
図2に示すように、レオメータ10は、固定プレート11と、この固定プレート11との隙間(例えば0.5mm)に試料となる接着剤3を挟み込む可動プレート12と、この可動プレート12を所定周期で回転振動させて接着剤3に応力を付与可能な駆動部13と、可動プレート12と同期して回転振動する円板部14と、プレート11,12と接着剤3を内部に収容して内部温度を昇降調節可能なケース部15と、円板部14の回転振動動作に基づき可動プレート12の周期を検出可能なエンコーダ16と、エンコーダ16の検出値に基づき駆動部13を制御すると共に可動プレート12に生じる粘性摩擦トルクを測定可能な制御測定部17と、ケース部15内部の温度を制御する温度制御部18と、制御測定部17と温度制御部18とを操作すると共に各種測定値を表示可能な操作部19を備えている。
損失弾性率G”は、次式(1)に動的粘性率η’を代入して算出することができる。尚、ωは角周波数である。
G”=ωη’ ・・・(1)
複素弾性率G*は、次式(2)に貯蔵弾性率G’と、式(1)で求めた損失弾性率G”を代入して算出している。尚、iは虚数単位である。
G*=G’+iG” ・・・(2)
複素粘度η*は、次式(3)に式(2)で求めた複素弾性率G*を代入して算出している。
η*=G*/(iω) ・・・(3)
式(1)〜式(3)から次式(4)を導くことができる。
η*=η’−iη” ・・・(4)
尚、複素粘度η*の虚部η”は、次式(5)で定義されるパラメータである。
η”=G’/ω ・・・(5)
下記表1に示す質量部数の各成分を用いて、下記の手順で構造用接着剤組成物を製造した。各材料を配合し、撹拌脱泡機HM−400WV(共立精機株式会社製)で2分間減圧攪拌脱泡し、構造用接着剤組成物を調製した。
*1)「DER331」Olin Corporation社製のビスフェノールA型液状エポキシ樹脂
*2)「HX−3088」旭化成社製のビスフェノールA型液状エポキシ樹脂2質量部中に、イミダゾール誘導体をエポキシ樹脂等の反応物で被覆した潜在性硬化促進剤1質量部が分散されている混合物
*3)「ダイハード 100SH」AlzChem社製のジシアンジアミド
*4)「PN−23」味の素ファインテクノ社製のエポキシ−イミダゾールアダクト系硬化剤
*5)「QC−X」井上石灰社製の酸化カルシウム
*6)「CML−31」近江化学社製の表面処理された酸化カルシウム
*7)「TS−720」キャボットジャパン社製のポリジメチルシロキサン処理されたヒュームドシリカ
*8)「L−07N」四国化成社製のホウ酸エステル化合物
*9)「NN#500」日東粉化工業社製の炭酸カルシウム
*10)「ED−502S」ADEKA社製の脂肪族モノグリシジルエーテル
得られた構造用接着剤組成物に塗布厚さ0.1mmにて100mm×25mm×1.6mmの冷間圧延鋼板に塗布し、2枚の鋼板の重ね合わせを12.5mmとし、はみ出た構造用接着剤組成物を除去して剪断試験片を作成した。試験片を130℃10分保持の条件で加熱硬化した後、24時間放冷し、その後、万能引張り試験機を用いて50mm/分の引張り速度で試験を行った。せん断強度が15MPa以上のものを○、15MPa未満のものを×と判定した。
得られた構造用接着剤組成物の粘度をブルックフィールド社製回転粘度計「RST−CPS」で初期(製造直後)及び50℃7日間貯蔵後の20℃における粘度を測定した。測定には直径25mmパラレルプレートを用いて、条件としてギャップ0.5mm、せん断速度0.2s−1と設定した。
得られた構造用接着剤組成物を40℃、湿度85%に4日間オープン放置し、図2に示したレオメータ10により20〜170℃まで毎分5℃の速度で昇温した際の複素粘度の最低値を測定した。測定には直径25mmパラレルプレートを用いて、条件としてギャップ0.5mm、周波数1Hz、歪み0.1%と設定した。
得られた構造用接着剤組成物を70mm×150mm厚さ0.8mmの冷間圧延鋼板の中央にφ4.5mmの半円ビード状に長さ130mm塗布して、40℃、湿度85%に4日間オープン放置し、ビードの上から15mm×150mm厚さ0.8mmの冷間圧延鋼板をスポット溶接し、電着塗装して150℃20分保持の条件で加熱硬化して、鋼板よりはみ出た構造用接着剤組成物の硬化物の発泡状態を判定した。溝欠陥がなく発泡が全くない物を◎、溝欠陥がなく発泡が5点以下の物を○、それ以上の発泡がある物または溝欠陥があるものを×と判定した。
一方、比較例1では低温で硬化できず、比較例2ではオープン放置後に高粘度となるためスポット溶接が不可能であり、比較例3では初期粘度が低すぎるためシャワー工程で飛び散るおそれがあり、比較例4では貯蔵後に増粘して塗布に支障があり、オープン放置後に溝欠陥ができる結果となった。
Claims (3)
- (A)エポキシ樹脂、
(B)マイクロカプセル化された硬化剤、
(C)吸湿剤、
(D)粘度調整剤、及び
(E)安定剤
を含み、
前記(C)吸湿剤が酸化カルシウムであり、表面処理品と表面非処理品の両方を含む、低温加熱硬化型構造用接着剤組成物。 - オープン放置後の、歪1%以下の動的粘弾性測定における温間中の複素粘度の最低値が200Pa・s以下である、請求項1記載の構造用接着剤組成物。
- 請求項1又は2記載の構造用接着剤組成物を被着体に塗布後、加熱硬化させる工程を含む、自動車構造体の製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017060693A JP6872944B2 (ja) | 2017-03-27 | 2017-03-27 | 低温加熱硬化型構造用接着剤組成物 |
US16/497,552 US11680193B2 (en) | 2017-03-27 | 2018-03-23 | Low-temperature heat-curable adhesive composition for structure |
RU2019134267A RU2727518C1 (ru) | 2017-03-27 | 2018-03-23 | Термоотверждаемая при низкой температуре адгезивная композиция для конструкций |
CN201880021061.2A CN110461981B (zh) | 2017-03-27 | 2018-03-23 | 低温加热固化型结构用粘接剂组合物 |
DE112018001618.8T DE112018001618T5 (de) | 2017-03-27 | 2018-03-23 | Bei niedriger Temperatur wärmehärtbare Klebstoffzusammensetzung für Struktur |
PCT/JP2018/011607 WO2018180955A1 (ja) | 2017-03-27 | 2018-03-23 | 低温加熱硬化型構造用接着剤組成物 |
MX2019011435A MX2019011435A (es) | 2017-03-27 | 2018-03-23 | Composicion adhesiva curable por calor a baja temperatura para estructura. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017060693A JP6872944B2 (ja) | 2017-03-27 | 2017-03-27 | 低温加熱硬化型構造用接着剤組成物 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2018162392A JP2018162392A (ja) | 2018-10-18 |
JP6872944B2 true JP6872944B2 (ja) | 2021-05-19 |
Family
ID=63675799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017060693A Active JP6872944B2 (ja) | 2017-03-27 | 2017-03-27 | 低温加熱硬化型構造用接着剤組成物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11680193B2 (ja) |
JP (1) | JP6872944B2 (ja) |
CN (1) | CN110461981B (ja) |
DE (1) | DE112018001618T5 (ja) |
MX (1) | MX2019011435A (ja) |
RU (1) | RU2727518C1 (ja) |
WO (1) | WO2018180955A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023189150A1 (ja) * | 2022-03-28 | 2023-10-05 | セメダイン株式会社 | 自動車構造体の製造方法及び硬化性組成物 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5855970A (ja) | 1981-09-29 | 1983-04-02 | 東芝ライテック株式会社 | 表示装置 |
JPS5883023A (ja) | 1981-11-11 | 1983-05-18 | Taoka Chem Co Ltd | 硬化性組成物 |
DE3750166T2 (de) | 1987-08-26 | 1995-02-23 | Asahi Chemical Ind | Härtemittel für ein härtbares Eintopfepoxidharzsystem. |
JPH0488077A (ja) * | 1990-07-31 | 1992-03-19 | Aisin Chem Co Ltd | スポット溶接可能な接着剤組成物 |
JP3199818B2 (ja) | 1992-03-06 | 2001-08-20 | 松本油脂製薬株式会社 | エポキシ樹脂硬化剤用マイクロカプセル |
JP3308347B2 (ja) | 1992-06-26 | 2002-07-29 | 日本化薬株式会社 | マイクロカプセル型硬化促進剤、これを含むエポキシ樹脂組成物及びその硬化物 |
JP2000281759A (ja) | 1999-04-01 | 2000-10-10 | Mitsui Chemicals Inc | 潜在性エポキシ硬化剤とそれを配合してなる1液型エポキシ樹脂組成物 |
DE60013181T2 (de) * | 1999-12-20 | 2005-08-11 | 3M Innovative Properties Co., Saint Paul | Bei umgebungstemperatur stabiler und einkomponentiger härtbarer epoxidharzklebstoff |
JP2001281759A (ja) | 2000-03-29 | 2001-10-10 | Seiko Epson Corp | 投影システム、投影装置および投影プログラムを記憶した記憶媒体 |
ATE510897T1 (de) * | 2007-04-11 | 2011-06-15 | Dow Global Technologies Llc | Hitzebeständige strukturelle epoxidharze |
JP2010189542A (ja) * | 2009-02-18 | 2010-09-02 | Cemedine Henkel Co Ltd | Ckd輸送対応ヘミング接着剤 |
JP5606079B2 (ja) * | 2010-01-19 | 2014-10-15 | ソマール株式会社 | エポキシ樹脂組成物及びこれを用いたディスペンサー塗布用接着剤 |
JP2011168672A (ja) * | 2010-02-17 | 2011-09-01 | Sekisui Chem Co Ltd | 絶縁シート |
EP2588554B1 (en) * | 2010-06-29 | 2014-11-19 | Dow Global Technologies LLC | Storage-stable heat-activated tertiary amine catalysts for epoxy resins |
WO2012000171A1 (en) * | 2010-06-29 | 2012-01-05 | Dow Global Technologies Llc | Storage-stable heat-activated tertiary amine catalysts for epoxy resins |
DE102011007893B4 (de) | 2011-04-12 | 2015-11-12 | Henkel Ag & Co. Kgaa | Thermobondingverfahren, Klebefilm, Verfahren zur Herstellung eines Klebefilms sowie dessen Verwendung |
KR102097069B1 (ko) * | 2012-03-23 | 2020-04-06 | 다우 글로벌 테크놀로지스 엘엘씨 | 난연성 구조용 에폭시 수지 접착제 및 금속 부재의 접합 방법 |
JP6013906B2 (ja) * | 2012-12-27 | 2016-10-25 | ナミックス株式会社 | 液状エポキシ樹脂組成物 |
US9976027B2 (en) | 2013-10-29 | 2018-05-22 | Kaneka Corporation | Polymer fine particle-containing curable resin composition having improved storage stability |
JP6191639B2 (ja) | 2015-03-18 | 2017-09-06 | マツダ株式会社 | 車体部材の接合構造及びその接合方法 |
-
2017
- 2017-03-27 JP JP2017060693A patent/JP6872944B2/ja active Active
-
2018
- 2018-03-23 DE DE112018001618.8T patent/DE112018001618T5/de active Pending
- 2018-03-23 MX MX2019011435A patent/MX2019011435A/es unknown
- 2018-03-23 US US16/497,552 patent/US11680193B2/en active Active
- 2018-03-23 WO PCT/JP2018/011607 patent/WO2018180955A1/ja active Application Filing
- 2018-03-23 CN CN201880021061.2A patent/CN110461981B/zh active Active
- 2018-03-23 RU RU2019134267A patent/RU2727518C1/ru active
Also Published As
Publication number | Publication date |
---|---|
RU2727518C1 (ru) | 2020-07-22 |
US20210102101A1 (en) | 2021-04-08 |
US11680193B2 (en) | 2023-06-20 |
CN110461981B (zh) | 2022-06-03 |
CN110461981A (zh) | 2019-11-15 |
DE112018001618T5 (de) | 2020-01-16 |
WO2018180955A1 (ja) | 2018-10-04 |
MX2019011435A (es) | 2019-12-19 |
JP2018162392A (ja) | 2018-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6422439B2 (ja) | 構造用接着フィルム | |
EP2529856B1 (en) | Metal Part Assembly And Method For Making Same | |
JP6612498B2 (ja) | エポキシ接着剤、並びに自動車用部材及びその製造方法 | |
EP0488949B1 (en) | High performance epoxy adhesive | |
JP7376473B2 (ja) | 接着剤組成物 | |
KR102341570B1 (ko) | 프리-겔 오븐용 에폭시 수지 조성물 | |
KR20070106534A (ko) | 2 성분 에폭시 접착제 조성물 | |
KR20180083413A (ko) | 파괴 모드가 개선된 구조 접착제 | |
EP2710049B1 (en) | Structural adhesive and use thereof | |
JP2004515565A (ja) | 耐衝撃性エポキシ樹脂組成物 | |
JP6872944B2 (ja) | 低温加熱硬化型構造用接着剤組成物 | |
JP7214418B2 (ja) | 接着性が向上した一剤熱硬化性エポキシ接着剤 | |
JP5739917B2 (ja) | 液状エポキシ樹脂組成物及びこれを用いた接着剤 | |
WO2018008742A1 (ja) | 加熱硬化により色が変化する構造用接着剤組成物 | |
JP6241589B2 (ja) | 硬化性樹脂組成物 | |
JP2017052922A (ja) | 自動車用接着剤 | |
JP5914123B2 (ja) | 電子部品用接着剤及び電子部品用接着フィルム | |
JP2015083638A (ja) | エポキシ樹脂接着剤組成物 | |
JP6020918B2 (ja) | 硬化性樹脂組成物 | |
JP2018087270A (ja) | エポキシ樹脂組成物 | |
JP2016056259A (ja) | エポキシ樹脂系接着剤組成物 | |
JP2015147903A (ja) | エポキシ系接着剤 | |
JPH01282212A (ja) | エポキシ樹脂組成物 | |
JPH0598230A (ja) | エポキシ樹脂系接着剤組成物 | |
JPH04335081A (ja) | エポキシ樹脂系接着剤組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20171122 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20171122 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191213 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201217 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210115 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210401 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210420 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6872944 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |