WO2021020506A1 - 接着剤セット及び接着体 - Google Patents
接着剤セット及び接着体 Download PDFInfo
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- WO2021020506A1 WO2021020506A1 PCT/JP2020/029218 JP2020029218W WO2021020506A1 WO 2021020506 A1 WO2021020506 A1 WO 2021020506A1 JP 2020029218 W JP2020029218 W JP 2020029218W WO 2021020506 A1 WO2021020506 A1 WO 2021020506A1
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- liquid
- adhesive
- mass
- meth
- acrylic monomer
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Links
- 239000007767 bonding agent Substances 0.000 title abstract 2
- 239000007788 liquid Substances 0.000 claims abstract description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims description 57
- 230000001070 adhesive effect Effects 0.000 claims description 57
- 239000000049 pigment Substances 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 16
- -1 methacryloyl Chemical group 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229940105570 ornex Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- IBARAOFMHIVQQI-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.COC(=O)C(C)=C.CCCCOC(=O)C=C IBARAOFMHIVQQI-UHFFFAOYSA-N 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 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 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer 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
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
Images
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
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Definitions
- This disclosure relates to an adhesive set and an adhesive body.
- a two-component adhesive using a (meth) acrylic monomer is known (for example, Patent Document 1).
- the polymerization of the (meth) acrylic monomer generally proceeds by a redox catalyst system formed by a polymerization initiator and a reducing agent, and as a result, the polymerization of the (meth) acrylic monomer proceeds.
- the adhesive cures.
- One aspect of the present invention is to provide a two-component adhesive which has sufficient curability at room temperature even in the presence of oxygen and suppresses dripping when applied to an adherend.
- One aspect of the present invention is a first liquid containing one or more acrylic monomers having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups, and epoxy groups and (meth).
- an adhesive set comprising a second liquid containing a curing agent containing a compound having a nucleophilic reactive group that reacts with any of the acryloyl groups.
- the acrylic monomer contains a bifunctional acrylic monomer having two (meth) acryloyl groups, and the ratio of the bifunctional acrylic monomer to the total mass of the acrylic monomer is 75% by mass or more.
- a two-component adhesive which has sufficient curability at room temperature even in the presence of oxygen and suppresses dripping when applied to an adherend.
- the adhesive set according to one aspect of the present invention may have excellent characteristics in terms of good ejection property from a nozzle or the like and a sufficiently long pot life.
- (meth) acryloyl means acryloyl or methacryloyl, and the same applies to other similar expressions.
- the adhesive set according to one embodiment is a two-component adhesive composed of a first liquid and a second liquid.
- the first liquid contains one or more acrylic monomers having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups.
- the second liquid contains a curing agent containing a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group.
- the acrylic monomer is a bifunctional or higher functional compound having an acryloyl group, a methacryloyl group, or both of them.
- the number of (meth) acryloyl groups contained in the acrylic monomer may be 2 to 4.
- the acrylic monomer contained in the first liquid is mainly composed of a bifunctional acrylic monomer having two (meth) acryloyl groups. Specifically, the ratio of the bifunctional acrylic monomer to the total mass of the acrylic monomer contained in the first liquid is 75% by mass or more. The ratio of the bifunctional acrylic monomer to the total mass of the acrylic monomer is 76% by mass or more, 77% by mass or more, 78% by mass or more, 79% by mass or more, 80% by mass or more, 81% by mass from the viewpoint of long pot life and the like.
- % Or more 82% by mass or more, 83% by mass or more, 84% by mass or more, 85% by mass or more, 86% by mass or more, 87% by mass or more, 88% by mass or more, 89% by mass or more, 90% by mass or more, 91% by mass % Or more, 92% by mass or more, 93% by mass or more, 94% by mass or more, 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, or 100% by mass. Good.
- the bifunctional acrylic monomer may be, for example, a poly (meth) acrylate of an aliphatic polyol.
- poly (meth) acrylates of aliphatic polyols include diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like.
- polyethylene polypropylene glycol di (meth) acrylate examples include diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like.
- polyethylene polypropylene glycol di (meth) acrylate examples include diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth
- bifunctional acrylic monomer examples include 2,2'-di (meth) acryloyloxydiethyl phosphate, ethylene oxide-modified di (meth) acrylate phosphate, urethane acrylate, and epoxy acrylate.
- examples of commercially available urethane acrylate products include EBECRYL230 (Dycel Ornex).
- Examples of commercially available epoxy acrylate products include EBECRYL230 (Dycel Ornex).
- the acrylic monomer may have two or more (meth) acryloyl groups and an epoxy group.
- compounds having two or more (meth) acryloyl groups and one or more epoxy groups are classified into bifunctional or polyfunctional acrylic monomers based on the number of (meth) acryloyl groups.
- the bifunctional acrylic monomer may be a compound having two (meth) acryloyl groups and no epoxy group.
- the first liquid may further contain a polyfunctional acrylic monomer having three or more (meth) acryloyl groups in addition to the bifunctional acrylic monomer.
- the polyfunctional acrylic monomer include trimethylolpropane tri (meth) acrylate, trifunctional (meth) acrylic monomer such as pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Examples include tetrafunctional (meth) acrylic monomers.
- the first liquid may further contain a monofunctional acrylic monomer having one (meth) acryloyl group.
- the proportion of the monofunctional acrylic monomer is 0 to 10% by mass, 0 to 5% by mass, 0 to 2% by mass, or 0 to 1% by mass with respect to the total amount of the bifunctional acrylic monomer and the polyfunctional acrylic monomer. May be good.
- the epoxy resin may be a bifunctional or higher epoxy resin.
- the number of epoxy groups contained in the epoxy resin may be 2 to 4.
- epoxy resins include diglycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol A type epoxy resin; phenol novolac.
- Novolak type epoxy resin such as type epoxy resin and cresol novolac type epoxy resin
- biphenyl type epoxy resin such as biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin
- polybasic acid for example, phthalic acid, dimer acid
- epichlorohydrin examples thereof include a glycidyl ester type epoxy resin which is a reaction product; a glycidyl amine type epoxy resin which is a reaction product of an amine compound (for example, p-aminophenol, diaminodiphenylmethane, isocyanuric acid) and epichlorohydrin; and an aliphatic epoxy resin.
- the epoxy resin may further have a (meth) acryloyl group.
- a compound having two or more epoxy groups and one (meth) acryloyl group is classified as an epoxy resin.
- the epoxy resin may be a compound having two or more epoxy groups and no (meth) acryloyl group.
- the first liquid may further contain a monofunctional acrylic monomer having one (meth) acryloyl group, a monofunctional epoxy resin having one epoxy group, or both of them.
- the content of the acrylic monomer having two or more (meth) acryloyl groups in the first liquid is the total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups. It may be 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, or 40 to 60% by mass.
- the total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups is 50 to 100% by mass and 60 to 100% by mass with respect to the amount of the first liquid. , 70-100% by mass, 80-100% by mass, 85-100% by mass or 90-100% by mass.
- the curing agent contained in the second liquid is a component that cures a mixture (adhesive) of the first liquid and the second liquid by reacting with an epoxy resin, an acrylic monomer, or both of them.
- the curing agent contains at least a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group. This compound may have 2 to 4 or 2 to 3 nucleophilic reactive groups.
- the nucleophilic reactive group may be, for example, an aliphatic amino group or a thiol group. From the viewpoint of reactivity with the (meth) acryloyl group, the nucleophilic reactive group may be an aliphatic amino group.
- examples of compounds having an aliphatic amino group include aliphatic amine compounds having two or more primary aliphatic amino groups, such as 1,3-bisaminomethylcyclohexane and 1,6-hexanediamine. Can be mentioned.
- Examples of commercially available products of compounds having an aliphatic amino group include jER Cure 3080 (manufactured by Mitsubishi Chemical Corporation, trade name).
- the curing agent contained in the second liquid may further contain a compound that substantially reacts only with the epoxy resin.
- a compound that substantially reacts only with the epoxy resin examples include aromatic amine compounds.
- the content of the compound having a nucleophilic reactive group in the second liquid is 30 to 100% by mass, 40 to 100% by mass, 50 to 100% by mass, 60 to 100% by mass, based on the amount of the second liquid. It may be 70 to 100% by mass, 80 to 100% by mass, 85 to 100% by mass, or 90 to 100% by mass.
- the first liquid, the second liquid, or both of them may further contain an inorganic filler.
- an inorganic filler By blending the inorganic filler, dripping when applied to the adherend can be suppressed more effectively.
- inorganic fillers include silica particles, calcium carbonate particles, and glass beads.
- the silica particles may be, for example, an unmodified silica filler, or a silica filler chain-modified with an alkyl chain, a (meth) acryloyl group, or the like.
- the content of the inorganic filler in the first liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the first liquid.
- the content of the inorganic filler in the second liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the second liquid.
- the content of the inorganic filler in the first liquid and the content of the inorganic filler in the second liquid may be the same or different.
- the first liquid, the second liquid, or both of them may further contain a silane coupling agent.
- the silane coupling agent may be, for example, a compound having a hydrolyzable silyl group and a functional group that reacts with at least one of an acrylic monomer, an epoxy resin or a curing agent.
- the hydrolyzable silyl group is, for example, a group having a silicon atom and 1 to 3 alkoxy groups bonded to the silicon atom.
- the number of carbon atoms of the alkoxy group bonded to the silicon atom may be, for example, 1 to 4.
- Examples of a functional group that reacts with at least one of an acrylic monomer or an epoxy resin include an amino group such as a primary amino group and a secondary amino group, an epoxy group, a mercapto group, and a (meth) acryloyl group. ..
- an amino group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a primary amino group and a secondary amino group
- an epoxy group such as a mercapto group
- silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
- KBM-303 KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503.
- the content of the silane coupling agent in the first liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the first liquid.
- the content of the silane coupling agent in the second liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the second liquid.
- the first liquid, the second liquid, or both of them may further contain other components if necessary.
- other components include pigments (eg carbon black, titanium oxide particles), and elastomers.
- the elastomer may be, for example, a triblock copolymer of methyl methacrylate-butyl acrylate-methyl methacrylate, a double-ended acrylate polymer, or a combination thereof.
- the content of the elastomer has one or more acrylic monomers having two or more (meth) acryloyl groups, an epoxy resin, and a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group. It may be 10 to 50% by mass, or 20 to 40% by mass, based on the total amount of the compound and the elastomer.
- both the first liquid and the second liquid may contain a pigment.
- both the first liquid and the second liquid may contain a pigment, and in that case, the pigment contained in the first liquid and the pigment contained in the second liquid may be different.
- the adhesive set contains a pigment in this way, when the first liquid and the second liquid are mixed, the mixed state of the first liquid and the second liquid can be visualized. By putting the mixed liquid of the first liquid and the second liquid in a mixed state in which the pigment is sufficiently uniformly dispersed, a better adhesive force tends to be obtained.
- FIG. 1 is a cross-sectional view showing an embodiment of an adhesive body.
- the adhesive body 30 shown in FIG. 1 has two adherends 11 and 12 and an adhesive layer 20 interposed between the two adherends 11 and 12 and adhering them.
- the adhesive layer 20 can be a cured product formed from the adhesive set according to the above-described embodiment.
- the adherend may be, for example, a molded body of metal such as steel, iron, copper, tinplate, aluminum, stainless steel, resin, or carbon fiber reinforced plastic (CFRP).
- the two or more adherends can be molded bodies of the same or different materials from each other.
- the method of obtaining an adhesive having two adherends using an adhesive set is, for example, arranging the two adherends with a gap, and the first liquid and the first liquid in the gap between the two adherends. It involves injecting a second solution and curing an adhesive that is a mixture of the first and second solutions.
- the first liquid and the second liquid may be mixed substantially at the same time as being injected into the gap between the two adherends, or may be mixed and then injected between the two adherends.
- the first liquid and the second liquid, or a mixture (adhesive) thereof, are injected between the two adherends using, for example, a mixing nozzle.
- the method of obtaining an adhesive is to apply an adhesive which is a mixture of the first liquid and the second liquid on one adherend, and to sandwich the applied adhesive between one adherend and the other. It may include affixing the adherend to the adherend and then curing the adhesive. As the adhesive cures, it forms an adhesive layer that intervenes between the two adherends and adheres them.
- the mixing ratio of the first liquid and the second liquid is determined by considering the stoichiometric ratio of the reaction between the acrylic monomer and epoxy resin contained in the first liquid and the curing agent contained in the second liquid. Adjusted to cure properly.
- the volume ratio of the first liquid to the second liquid may be 0.5 to 5.0.
- Curing conditions are adjusted so that the adhesive cures properly.
- the adhesive may be cured in an environment of 10 to 40 ° C.
- the curing time is adjusted, for example, between 1 hour and 1 week.
- the adhesive may be heated, in which case the heating temperature may be, for example, 40-120 ° C.
- the adhesive set was evaluated by the following method. The evaluation results are shown in Tables 1 and 2. (1) Dripping The first liquid and the second liquid were mixed at a volume ratio of 2: 1 using a static mixer, and the formed adhesive was applied onto a vertically standing aluminum plate. The state of dripping of the adhesive mixture after application was observed, and the time from the time of application to the occurrence of dripping of 1.0 mm or more was measured. From the measurement results, each adhesive set was evaluated according to the following evaluation criteria. A: 30 minutes or more B: More than 10 minutes and less than 30 minutes C: Within 10 minutes
- Adhesive body 11, 12 ... Adhesive body, 20 ... Adhesive layer, 30 ... Adhesive body.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
以下の各原料を用いて、表1又は表2に示す組成の第一液及び第二液を調製した。
(1)アクリルモノマー
(2官能アクリルモノマー)
・1,6-ヘキサンジオールジアクリレート(製品名:ビスコート230、新中村化学工業株式会社)
(3官能アクリルモノマー)
・トリメチロールプロパントリアクリレート(製品名:TMPTA、ダイセル・オルネクス株式会社)
(4官能アクリルモノマー)
・ジトリメチロールプロパンテトラアクリレート(製品名:EBECRYL140、ダイセル・オルネクス株式会社)
(2)エポキシ樹脂
・ビスフェールF型エポキシ樹脂(製品名:EPICLON830、DIC株式会社)
(3)硬化剤
・1,3-ビスアミノメチルシクロヘキサン
・脂肪族アミン系硬化剤(製品名:jERキュア3080、三菱ケミカル株式会社)
(4)フィラー(無機充填剤)
・シリカ粒子(製品名:アエロジル200V、日本アエロジル株式会社)
(5)シランカップリング剤
・3-グリシジルオキシプロピルトリメトキシシラン(製品名:KBM-403、信越化学工業株式会社)
・3-アミノプロピルトリメトキシシラン(製品名:KBM-903、信越化学工業株式会社)
(6)エラストマー
・メチルメタクリレート-ブチルアクリレート-メチルメタクリレートのトリブロック共重合体(製品名:クラリティLA3320又はLA2140、株式会社クラレ)
・両末端アクリレートポリマー(製品名:XMAP RC110C又はRC310C、株式会社カネカ)
以下の方法により接着剤セットを評価した。表1及び表2に評価結果を示す。
(1)液だれ
スタティックミキサーを用いて第一液と第二液とを体積比2:1で混合し、形成された接着剤を、垂直に立てたアルミニウム板上に塗布した。塗布後の接着剤混合物の液だれの状態を観察し、塗布の時点から1.0mm以上の液だれが発生するまでの時間を測定した。測定結果から、以下の評価基準で各接着剤セットを評価した。
A:30分以上
B:10分を超えて30分未満
C:10分以内
スタティックミキサーを用いて第一液と第二液とを体積比2:1で混合し、形成された接着剤をアルミニウム板上に塗布した。塗布された接着剤を、空気環境下、25℃で1日養生した時点で、接着剤が硬化したか否かを目視で確認した。硬化が確認された接着剤を「A」、硬化が確認されなかった接着剤を「C」と判定した。
スタティックミキサーを用いて第一液と第二液とを体積比2:1で混合し、形成された接着剤をアルミニウム板上に塗布した。塗布された接着剤を25℃で30分静置した。その後、接着剤をもう一枚のアルミニウム板で挟み、形成された積層体を25℃で3日間養生した。養生後、2枚のアルミニウム板の間の接着強度(せん断強度)を測定した。せん断強度が大きいことは、可使時間が大きいことを意味する。せん断強度の値に基づいて、以下の基準で可使時間を判定した。
A:せん断強度が8MPa以上
B:せん断強度が4MPa以上8MPa未満
C:せん断強度が4MPa未満
Claims (6)
- 2個以上の(メタ)アクリロイル基を有する1種以上のアクリルモノマー、及び2個以上のエポキシ基を有するエポキシ樹脂を含有する第一液と、
エポキシ基及び(メタ)アクリロイル基のいずれもと反応する求核性反応基を有する化合物を含む硬化剤を含有する第二液と、を備え、
前記アクリルモノマーが2個の(メタ)アクリロイル基を有する二官能アクリルモノマーを含み、前記アクリルモノマーの全体質量に対する前記二官能アクリルモノマーの割合が75質量%以上である、
接着剤セット。 - 前記求核性反応基が脂肪族アミノ基である、請求項1に記載の接着剤セット。
- 前記第一液又は前記第二液のうち少なくとも一方が無機充填剤を更に含有する、請求項1又は2に記載の接着剤セット。
- 前記第一液又は前記第二液のうち一方のみが顔料を更に含有する、請求項1~3のいずれか一項に記載の接着剤セット。
- 前記第一液及び前記第二液がそれぞれ顔料を更に含有し、前記第一液が含有する顔料と前記第二液が含有する顔料とが異なる、請求項1~4のいずれか一項に記載の接着剤セット。
- 2以上の被着体と、前記2以上の被着体を接着する接着層と、を有し、
前記接着層が、請求項1~5のいずれか一項に記載の接着剤セットによって形成された層である、接着体。
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JP2017519869A (ja) * | 2014-06-17 | 2017-07-20 | スリーエム イノベイティブ プロパティズ カンパニー | 速硬化性エポキシ接着剤組成物 |
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2019
- 2019-07-31 WO PCT/JP2019/030072 patent/WO2021019741A1/ja active Application Filing
-
2020
- 2020-07-30 WO PCT/JP2020/029218 patent/WO2021020506A1/ja active Application Filing
- 2020-07-30 TW TW109125857A patent/TW202112992A/zh unknown
- 2020-07-30 JP JP2021535422A patent/JPWO2021020506A1/ja active Pending
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US4051195A (en) * | 1975-12-15 | 1977-09-27 | Celanese Polymer Specialties Company | Polyepoxide-polyacrylate ester compositions |
JPH0195176A (ja) * | 1987-09-03 | 1989-04-13 | Texaco Dev Corp | エポキシ接着剤 |
JPH08295864A (ja) * | 1995-02-27 | 1996-11-12 | Asahi Chem Ind Co Ltd | 建築構造物用固着剤 |
JPH08325358A (ja) * | 1995-06-02 | 1996-12-10 | Toyo Ink Mfg Co Ltd | 土木建築材料用硬化性樹脂組成物 |
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