WO2023286709A1 - 2-cyanoacrylate adhesive composition - Google Patents
2-cyanoacrylate adhesive composition Download PDFInfo
- Publication number
- WO2023286709A1 WO2023286709A1 PCT/JP2022/027096 JP2022027096W WO2023286709A1 WO 2023286709 A1 WO2023286709 A1 WO 2023286709A1 JP 2022027096 W JP2022027096 W JP 2022027096W WO 2023286709 A1 WO2023286709 A1 WO 2023286709A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cyanoacrylate
- adhesive composition
- recovery rate
- elongation recovery
- compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 120
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004830 Super Glue Substances 0.000 title claims abstract description 84
- -1 2-cyanoacrylate compound Chemical class 0.000 claims abstract description 298
- 229920005862 polyol Polymers 0.000 claims abstract description 74
- 150000003077 polyols Chemical class 0.000 claims abstract description 66
- 229920001651 Cyanoacrylate Polymers 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims description 116
- 239000000853 adhesive Substances 0.000 claims description 42
- 230000001070 adhesive effect Effects 0.000 claims description 42
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 16
- 229920001195 polyisoprene Polymers 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 229920005906 polyester polyol Polymers 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 19
- 229920001451 polypropylene glycol Polymers 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000012856 packing Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 238000007664 blowing Methods 0.000 description 8
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
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- 229920001577 copolymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 3
- GVZVYNDABXTXIP-UHFFFAOYSA-N 3-cyanoprop-2-enoyl chloride Chemical compound ClC(=O)C=CC#N GVZVYNDABXTXIP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000003136 n-heptyl 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])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 2
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- RYPWYUBFPYHUSR-UHFFFAOYSA-N C(#N)C(C(=O)OCCOCCOCC(CCCC)CC)=C Chemical compound C(#N)C(C(=O)OCCOCCOCC(CCCC)CC)=C RYPWYUBFPYHUSR-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- HAFJKEBDIQTCEH-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl 2-cyanoprop-2-enoate Chemical compound CCCCOCCOCCOC(=O)C(=C)C#N HAFJKEBDIQTCEH-UHFFFAOYSA-N 0.000 description 1
- BOSXZNXZBFCZQM-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)COC(C)CO.CC(O)COC(C)CO BOSXZNXZBFCZQM-UHFFFAOYSA-N 0.000 description 1
- CUEJHYHGUMAGBP-UHFFFAOYSA-N 2-[2-(1h-indol-5-yl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1C1=CC=C(NC=C2)C2=C1 CUEJHYHGUMAGBP-UHFFFAOYSA-N 0.000 description 1
- LIIGSIGMAHCMQM-UHFFFAOYSA-N 2-ethylhexyl cyclohexanecarboxylate Chemical compound CCCCC(CC)COC(=O)C1CCCCC1 LIIGSIGMAHCMQM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
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- CZFVEVXXJWQRQV-UHFFFAOYSA-N C(#N)C(=CC(=O)OCCCCCCCCCCCCO)C#N Chemical compound C(#N)C(=CC(=O)OCCCCCCCCCCCCO)C#N CZFVEVXXJWQRQV-UHFFFAOYSA-N 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
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- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
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- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 125000006229 isopropoxyethyl group Chemical group [H]C([H])([H])C([H])(OC([H])([H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Definitions
- the present disclosure relates to a 2-cyanoacrylate adhesive composition.
- An adhesive composition containing a 2-cyanoacrylate compound initiates polymerization due to a weak anion such as a slight amount of moisture adhering to the surface of an adherend due to the unique anionic polymerizability of the 2-cyanoacrylate compound. Materials can be firmly joined in a short time. Therefore, it is used as a so-called instant adhesive in a wide range of fields such as industrial, medical and household use.
- Japanese Patent No. 5267571 discloses a 2-cyanoacrylate ester and a polyfunctional cyanoacrylate ester having two or more 2-cyanoacryloyl groups.
- the number average molecular weight of the (b) polyfunctional cyanoacrylic acid ester is 1,000 to 50,000 and the 2-cyanoacrylic acid ester is 100 parts by mass.
- the (b) polyfunctional cyanoacrylic acid ester is proposed to be 1 to 400 parts by mass of an adhesive composition.
- the adhesive composition is required to have good deformation (elongation recovery rate) from the stretched cured product to the cured product in the state before stretching.
- the present inventors have now found that there is room for further improvement in the elongation recovery rate of the cured product of the adhesive composition disclosed in Japanese Patent No. 5267571.
- a cured product obtained by homopolymerizing a 2-cyanoacrylate compound has a storage elastic modulus at 25° C. of greater than 1.0 ⁇ 10 7 Pa and not more than 5.0 ⁇ 10 7 Pa
- the above Polyfunctional cyanoacrylate compounds include polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, 2-cyanoacrylate compounds of hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl formal , polyvinyl butyral, polyvinyl alcohol, phenolic resin, a silane compound having hydroxyl groups at both ends, and a siloxane compound having hydroxyl groups at both ends.
- the inventors have found that the cured product obtained from the adhesive composition has an excellent elongation recovery rate compared to the adhesive composition that does not contain the
- the problem to be solved by the present disclosure is to provide a 2-cyanoacrylate-based adhesive composition that exhibits an excellent elongation recovery rate of the cured product.
- Means for solving the above problems include the following aspects. ⁇ 1> A cured product obtained by homopolymerizing the 2-cyanoacrylate compound and containing a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound has a storage modulus at 25° C. of 1.0 ⁇ 10 7 Pa or more.
- the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic 2-cyanoacrylic acid of a compound selected from the group consisting of polyols, polyurethane polyols, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resins, silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends A 2-cyanoacrylate adhesive composition containing at least one ester.
- ⁇ 2> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The 2-cyanoacrylate adhesive composition according to ⁇ 1> above, wherein the length (L2) between the two is measured, and the elongation recovery rate (%) obtained from the following formula (1) is 55% or more.
- a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. 2.
- Elongation recovery rate (%): ⁇ (L1-L3) / (L1-L0) ⁇ ⁇ 100 (2) (LB-Lb/Lb) ⁇ 100 ⁇ 50% (B) ⁇ 6>
- a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 30 minutes passed, the marking 2.
- L 1 each independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )-;
- R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent;
- R 2 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent;
- p represents an integer of 1 to 5; ⁇ 11> Any of the above ⁇ 1> to ⁇ 10>, wherein the cured product obtained by homopolymerizing the 2-cyanoacrylate compound has a maximum loss tangent value (tan ⁇ (max)) of 80°C or less.
- 2-cyanoacrylate adhesive composition according to any one of the above.
- the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
- the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
- the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
- a combination of two or more preferred aspects is a more preferred aspect.
- the 2-cyanoacrylate-based adhesive composition of the present disclosure contains a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, and stores the cured product obtained by homopolymerizing the 2-cyanoacrylate compound at 25°C.
- the elastic modulus is greater than 1.0 ⁇ 10 7 Pa and 5.0 ⁇ 10 7 Pa or less
- the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, The group consisting of polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends at least one 2-cyanoacrylate ester of a compound selected from
- the 2 - cyanoacrylate adhesive composition is a 2 - cyanoacrylate compound (
- a cured product obtained by homopolymerizing a 2-cyanoacrylate compound is also referred to as a homopolymer)
- polyoxyalkylene polyol polyol
- polyester polyol polycarbonate polyol
- polybutadiene polyol hydrogenated polybutadiene polyol
- polyisoprene polyol hydrogenated poly 2 of compounds selected from the group consisting of isoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends -
- the 2-cyanoacrylate adhesive composition of the present disclosure has a storage modulus at 25° C. of a cured product obtained by homopolymerization of 2-cyanoacrylate having a storage modulus of more than 1.0 ⁇ 10 7 Pa and not more than 5.0 ⁇ 10 7 Pa.
- a specific 2-cyanoacrylate compound an acrylate compound (hereinafter also referred to as a specific 2-cyanoacrylate compound).
- the 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds.
- the storage elastic modulus of the homopolymer at 25° C. is preferably 1.1 ⁇ 10 7 Pa to 4.0 ⁇ 10 7 Pa, more preferably 1.2 ⁇ 10 7 Pa. It is more preferably ⁇ 3.0 ⁇ 10 7 Pa.
- the storage modulus of a cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound is measured as follows. After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using the dynamic viscoelasticity measuring device, the storage elasticity was measured under the conditions of a frequency of 1 Hz, a temperature of 25 ° C., and a thickness of 300 ⁇ m. measure the rate. After confirming that the storage modulus of the 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the 2-cyanoacrylate compound. Next, using the cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C.
- the temperature at which the cured product obtained by homopolymerizing the specific 2-cyanoacrylate compound shows the maximum loss tangent value is preferably 80° C. or less. It is more preferably 77° C. or lower. Although the lower limit of the temperature is not particularly limited, it can be, for example, 50° C. or higher.
- the temperature at which the loss tangent of a specific 2-cyanoacrylate compound exhibits a maximum value is measured as follows. After injecting the specific 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, the dynamic viscoelasticity measuring device was used to store the compound under the conditions of a frequency of 1 Hz, a temperature of 25°C, and a thickness of 300 ⁇ m. Measure the elastic modulus. After confirming that the storage modulus of the specific 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the specific 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C.
- the dynamic viscoelasticity measuring device that can be used is as described above.
- the specific 2-cyanoacrylate compound preferably has an ether bond from the viewpoint of the elongation recovery rate of the cured product. Further, from the same viewpoint, the specific 2-cyanoacrylate compound preferably has 2 or more ether bonds, more preferably 2 to 5, even more preferably 2 to 4, and 2 Or it is particularly preferable to have three.
- the 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds having different numbers of ether bonds.
- the specific 2-cyanoacrylate compound preferably contains a compound represented by the following formula (1).
- each L 1 independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- , -CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- is preferable from the viewpoint of the elongation recovery rate of the cured product, and -CH 2 CH 2 - is more preferable.
- R 1 represents an optionally substituted alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
- substituents include aryl groups, halogen atoms, alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, and acyloxy groups.
- R 1 include a methyl group, an ethyl group, a propyl group, and the like, and from the viewpoint of the elongation recovery rate of the cured product, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
- R 2 represents an optionally substituted alkyl group having 1 to 15 carbon atoms, and may be a linear alkyl group or a branched alkyl group.
- substituents described above for R 1 include the substituents described above for R 1 .
- R 2 in formula (1) is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 4 to 13 carbon atoms, from the viewpoint of the elongation recovery rate of the cured product, and more preferably an alkyl group having 4 to 13 carbon atoms. 10 alkyl groups are more preferred.
- R 2 in formula (1) includes 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group and 2-methylheptyl.
- a 2-ethylhexyl group or an n-butyl group is preferable from the viewpoint of the elongation recovery rate of the product.
- p represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, from the viewpoint of the elongation recovery rate of the cured product, 2 is more preferred.
- R 2 is a 2-ethylhexyl group, 2 -methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-methylheptyl group, 2-ethylpentyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-h
- R 2 is 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-methyl heptyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-
- the compound represented by formula (1) include 2-(2-ethylhexyloxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-(1-methylbutoxy)ethyl, 2-(2- Ethylbutoxy)ethyl, 2-(2-methylbutoxy)ethyl, 2-pentyloxyethyl, 2-(2-methylpentyloxy)ethyl, 2-(2-ethylpentyloxy)ethyl, 2-(2-methylhexyl oxy)ethyl, 2-(2-methylheptyloxy)ethyl, 2-hexyloxyethyl, 2-(1-methylpentyloxy)ethyl, 2-heptyloxyethyl, 2-(1-methylhexyloxy)ethyl, 2 -(1-ethylpentyloxy)ethyl, 2-octyloxyethyl, 2-(1-methylheptyloxy)
- 2-(2-ethylhexyloxy)ethyl-2-cyanoacrylate 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2 -(2-butoxyethoxy)ethyl-2-cyanoacrylate is preferred, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2-(2-butoxyethoxy)ethyl-2-cyanoacrylate 2-cyanoacrylate esters of are more preferred.
- the content of the specific 2-cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate adhesive composition is preferably 50 parts by mass or more, and is 60 parts by mass or more. more preferably 70 parts by mass or more, particularly preferably 75 parts by mass or more, and most preferably 80 parts by mass or more.
- the upper limit of the content of the specific 2-cyanoacrylate compound is not particularly limited, but can be, for example, 90 parts by mass or less.
- the specific 2-cyanoacrylate compound contains the compound represented by formula (1)
- the specific 2-cyanoacrylate compound contained in the 2-cyanoacrylate-based adhesive composition from the viewpoint of the elongation recovery rate of the cured product.
- the content of the compound represented by formula (1) with respect to 100 parts by mass is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, It is particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
- the 2-cyanoacrylate adhesive composition of the present disclosure includes polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl Formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, at least one 2-cyanoacrylic acid ester of a compound selected from the group consisting of silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends.
- the polyfunctional cyanoacrylate compound preferably contains a 2-cyanoacrylate ester of a compound selected from the group consisting of polyoxyalkylene polyols and acrylic polyols. More preferably, it contains a 2-cyanoacrylate ester of an oxyalkylene polyol.
- the polyfunctional cyanoacrylate compound means a compound having two or more cyanoacryloyl groups.
- the polyoxyalkylene polyol is not particularly limited, but includes polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, polyoxy Tetramethylene glycol, etc., and copolymers with polyols or other glycols, etc. can be used.
- the polyester polyol is not particularly limited, but general polyester polyol produced by reaction of dibasic acid such as adipic acid with glycol, triol, etc., polycaprolactone polyol obtained by ring-opening polymerization of caprolactone. etc. can be used.
- the polycarbonate polyol is not particularly limited, but a general polycarbonate diol derived from ethylene carbonate or the like, a copolymer of carbonate and glycol, and the like can be used.
- Polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and 2-cyanoacrylate of hydrogenated polyisoprene polyol are preferable from the viewpoint of hot water resistance in addition to the flexibility and toughness of the cured product.
- the polyfunctional cyanoacrylate compound preferably contains a cyanoacrylate ester having 2 to 12 functional groups, and more preferably contains a cyanoacrylate ester having 2 to 6 functional groups. It preferably contains a cyanoacrylate having 2 to 4 functional groups, and particularly preferably contains a cyanoacrylate having 2 or 3 functional groups (bis-cyanoacrylate compound or tris-cyanoacrylate compound). From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains at least one of biscyanoacrylate and triscyanoacrylate.
- the biscyanoacrylate is preferably a polyoxyalkylene polyol biscyanoacrylate or an alkanediol biscyanoacrylate.
- the triscyanoacrylate is preferably a polyoxyalkylene polyol tricyanoacrylate.
- Polyoxyalkylene polyols constituting the polyoxyalkylene polyol biscyanoacrylate compound or polyoxyalkylene polyol tricyanoacrylate include polyoxypropylene glycol (PPG), polyoxyethylene glycol, polyoxytetramethylene glycol, polyoxy Examples include ethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol and the like. Among them, polyoxypropylene glycol (PPG)-biscyanoacrylate or polyoxypropylene glycol (PPG)-triscyanoacrylate is preferable from the viewpoint of elongation recovery rate of the cured product.
- alkanediol biscyanoacrylates include 1,6-hexanediol-biscyanoacrylate, 1,4-butanediol-biscyanoacrylate, 1,8-octanediol-biscyanoacrylate, 1,9-nonanediol- biscyanoacrylate, 1,10-decanediol-biscyanoacrylate, 1,12-dodecanediol-biscyanoacrylate and the like.
- the molecular weight or number average molecular weight (Mn) of the polyfunctional cyanoacrylate compound is preferably 1,000 to 50,000, more preferably 1,000 to 10,000. It is more preferably 1,000 to 5,000.
- Mn is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
- the content of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure is 2 parts by mass to 50 parts by mass. It is preferably 7 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 20 parts by mass, and particularly preferably 13 parts by mass to 18 parts by mass. 14 parts by mass to 17 parts by mass is most preferred.
- polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, relative to 100 parts by mass of polyfunctional cyanoacrylate contained in the 2-cyanoacrylate adhesive composition The sum of the contents of the 2-cyanoacrylate compounds in the compounds selected from the group consisting of polyisoprene polyols and hydrogenated polyisoprene polyols is preferably 70 parts by mass or more, more preferably 80 parts by mass or more. , more preferably 90 parts by mass or more, particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
- the 2-cyanoacrylate-based adhesive composition of the present disclosure may contain components other than the specific 2-cyanoacrylate compound and the polyfunctional cyanoacrylate compound within a range that does not impair its properties.
- Other components include 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds, stabilizers, curing accelerators, plasticizers, thickeners, particles, colorants, fragrances, solvents, strength improvers, and the like. .
- 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n- Pentyl, n-hexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl, 2-ethylhexyl, n-octyl, 2-octyl, n-nonyl, oxononyl, n-decyl, n-dodecyl, methoxyethyl, methoxypropyl, methoxyisopropyl , methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxyisopropyl, propoxymethyl, propoxyethyl, isopropoxyethyl,
- Stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and trifluorides such as boron trifluoride methanol and boron trifluoride diethyl ether.
- examples include boron complexes, anionic polymerization inhibitors such as HBF 4 and trialkylborate, and radical polymerization inhibitors such as (2) hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol and pyrogallol. These stabilizers may be used alone or in combination of two or more.
- Curing accelerators include polyether compounds, calixarenes, thiacalixarenes, pyrogallolarenes, onium salts and the like. One of these curing accelerators may be used alone, or two or more thereof may be used in combination.
- Plasticizers include acetyl triethyl citrate, acetyl tributyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and phthalate.
- diheptyl acid dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl) camphorate, 2 -ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, caproic acid triglyceride, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate and the like.
- acetyl tributyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate or dipropylene glycol dipropylene glycol are preferred because of their good compatibility with 2-cyanoacrylate compounds and high plasticization efficiency. Benzoates are preferred. These plasticizers may be used alone or in combination of two or more.
- thickeners examples include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic acid esters, copolymers of methyl methacrylate and other methacrylic acid esters, acrylic rubber, polyvinyl acetate, polyvinyl chloride, Polyurethane resins, polyamide resins, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylic acid esters, ethylene-vinyl acetate copolymers, and the like. These thickeners may be used alone or in combination of two or more.
- the 2-cyanoacrylate-based adhesive composition of the present disclosure may contain particles to the extent that the properties thereof are not impaired, and are thus formed by using the 2-cyanoacrylate-based adhesive composition.
- the thickness of the adhesive layer can be adjusted.
- the average particle diameter of the particles is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 200 ⁇ m, even more preferably 15 ⁇ m to 150 ⁇ m.
- the material of the particles is not particularly limited as long as it is insoluble in the 2-cyanoacrylate compound or the like used and does not cause deterioration such as polymerization.
- Particles include thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, and polyphenylene oxide; unsaturated polyesters, divinylbenzene polymers, Crosslinked resins such as divinylbenzene-styrene copolymers, divinylbenzene-(meth)acrylate copolymers, and diallyl phthalate polymers; inorganic compounds such as spherical silica, glass beads, and glass fibers; silicone compounds; Examples include organic-inorganic composite particles containing a polysiloxane skeleton.
- thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulf
- the content of the particles is not particularly limited, but from the viewpoint of curing speed, adhesive strength, etc., the amount of particles per 100 mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure.
- the content is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, even more preferably 1 to 3 parts by mass.
- the average particle diameter of particles is a volume-based average value measured by a laser diffraction particle size distribution analyzer.
- a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after one minute has passed
- the length (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is preferably 55% or more, more preferably 58% or more, and 60% or more.
- the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L2) / (L1-L0) ⁇ ⁇ 100 (1)
- a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 5 minutes
- the length (L3) is measured, and the elongation recovery rate (%) obtained from the following formula (2) is preferably 65% or more, more preferably 67% or more, and 70% or more. is more preferable, and 75% or more is particularly preferable.
- the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L3) / (L1-L0) ⁇ ⁇ 100 (2)
- a cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 30 minutes
- the length (L4) is measured, and the elongation recovery rate (%) obtained from the following formula (3) is preferably 70% or more, more preferably 73% or more, and 75% or more. is more preferable, and 80% or more is particularly preferable.
- the elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity. Elongation recovery rate (%): ⁇ (L1-L4) / (L1-L0) ⁇ ⁇ 100 (3)
- a Strograph V20-C manufactured by Toyo Seiki Seisakusho Co., Ltd. or a similar device can be used.
- the cured product used for the measurement of the elongation recovery rate is produced as follows. First, a silicone rubber mold with a thickness of 1 mm is placed on a release polyethylene terephthalate (PET) film. Next, 1 ⁇ L of triethanolamine is added to 1 g of the 2-cyanoacrylate-based adhesive composition of the present disclosure, stirred, and poured into the mold.
- the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and then at a temperature of 25 ° C. and a relative humidity of 50%. Allow 24 hours to fully cure. After curing, the mold and release PET film are removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
- the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (1) is LA
- La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured
- the following formula (A) is preferably satisfied. (LA ⁇ La/La) ⁇ 100 ⁇ 50% (A)
- LB is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (2)
- the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb
- the following formula (B) is preferably satisfied. (LB-Lb/Lb) ⁇ 100 ⁇ 50% (B)
- the 2-cyanoacrylate adhesive composition of the present disclosure can be used in various applications such as construction applications, automobile-related applications, and electrical/electronic material applications.
- Architectural applications include elastic adhesives for construction, adhesives for double glazing, adhesives for artificial marble, and the like.
- Examples of electrical/electronic material applications include resins for encapsulating semiconductors, insulating materials for printed wiring boards, insulating coating materials for electric wires and cables, electronic component coating agents, electronic component potting agents, electrical component sealers, and the like.
- the 2-cyanoacrylate adhesive composition of the present disclosure can also be used for packings, O-rings and the like.
- waterproof packings Specifically, waterproof packings, insect-proof packings, anti-vibration/sound absorption and air seal materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater packings, electrode packings, safety valve diaphragms, solenoid valves, Waterproof packing for steam oven ranges and jar rice cookers, water tank packing, water absorption valves, water receiving packing, heat insulation heater packing, oil packing for combustion equipment such as steam outlet seals, O-rings, drain packing, feed/intake packing, Anti-vibration rubber, oil fill port packing, oil gauge packing, diaphragm valve, etc., speaker gasket for audio equipment, speaker edge, etc.
- the adhesive composition of the present invention can be used in a gasket method [MIPG (Mold In Place Gasket), FIPG (Mold In Place Gasket), FIPG ( Formed In Place Gasket), CIPG (Cured In Place Gasket)].
- 2-cyanoacrylate-based adhesive composition of the present disclosure can be suitably used for resins or metals as adherends, and can be more suitably used for rubber.
- the storage elastic modulus at 25°C was determined.
- the storage elastic modulus at 25° C. of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example is shown. summarized in 1.
- Example 1 To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
- PPG4000TCA was synthesized by the following method.
- a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene.
- the reaction system was heated to 60° C., and while blowing nitrogen gas from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; Polyether G-4000"] dissolved in 16 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
- PPG3000BCA was synthesized by the following method.
- a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the reaction system was heated to 60° C., and while blowing nitrogen gas through a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; ADEKA POLYOL P-3000"] dissolved in 18 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
- PPG10000BCA was synthesized by the following method.
- a 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the temperature of the reaction system is raised to 60° C., and while nitrogen gas is blown from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; A solution of 94.5 g of Preminol S-4011"] dissolved in 60 mL of benzene was added. The temperature was then maintained at 60° C. and stirred for 30 minutes.
- elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 94%, and 90%, respectively.
- 2-cyanoacrylate adhesive composition produced in Example 3 in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 91% and 85%, respectively.
- the 2-cyanoacrylate adhesive compositions produced in Examples are excellent in the rate of increase in elongation recovery rate of the cured product.
- the recovery of elongation of the cured product has progressed greatly 5 minutes after the fixation of the jig was released.
- the rate of increase in the elongation recovery rate at 30 minutes after the release was smaller than the rate of increase in elongation recovery rate at the time of 5 minutes.
- Table 1 summarizes the rate of increase in the elongation recovery rate of each example and comparative example. Comparative Examples 1 to 4 and Comparative Example 8, which serve as the reference for the rate of increase in elongation recovery rate, are all listed as "1" in Table 1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A 2-cyanoacrylate adhesive composition comprising a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, wherein the storage modulus at 25°C of a cured product obtained by homopolymerization of the 2-cyanoacrylate compound is higher than 1.0×107 Pa but no higher than 5.0×107, and the polyfunctional cyanoacrylate compound contains at least one 2-cyanoacrylate compound of a compound selected from the group consisting of polyoxyalkylene polyols and the like.
Description
本開示は、２－シアノアクリレート系接着剤組成物に関する。
The present disclosure relates to a 2-cyanoacrylate adhesive composition.
２－シアノアクリレート化合物を含有する接着剤組成物は、２－シアノアクリレート化合物が有する特異なアニオン重合性により、被着体表面に付着する僅かな水分等の微弱なアニオンによって重合を開始し、各種材料を短時間で強固に接合することができる。そのため、いわゆる、瞬間接着剤として、工業用、医療用、家庭用等の広範な分野において用いられている。
An adhesive composition containing a 2-cyanoacrylate compound initiates polymerization due to a weak anion such as a slight amount of moisture adhering to the surface of an adherend due to the unique anionic polymerizability of the 2-cyanoacrylate compound. Materials can be firmly joined in a short time. Therefore, it is used as a so-called instant adhesive in a wide range of fields such as industrial, medical and household use.
２－シアノアクリレート化合物を含有する接着剤組成物として、特許第５２６７５７１号公報には、２－シアノアクリル酸エステルと、２－シアノアクリロイル基を２個以上有する多官能シアノアクリル酸エステルと、を含有する接着剤組成物であって、上記（ｂ）多官能シアノアクリル酸エステルの数平均分子量が１，０００～５０，０００であり、且つ上記２－シアノアクリル酸エステルを１００質量部とした場合に、該（ｂ）多官能シアノアクリル酸エステルは１質量部～４００質量部である接着剤組成物が提案されている。
As an adhesive composition containing a 2-cyanoacrylate compound, Japanese Patent No. 5267571 discloses a 2-cyanoacrylate ester and a polyfunctional cyanoacrylate ester having two or more 2-cyanoacryloyl groups. When the number average molecular weight of the (b) polyfunctional cyanoacrylic acid ester is 1,000 to 50,000 and the 2-cyanoacrylic acid ester is 100 parts by mass. , the (b) polyfunctional cyanoacrylic acid ester is proposed to be 1 to 400 parts by mass of an adhesive composition.
ここで、接着剤組成物には、その用途によっては、伸長させた硬化物の伸長前の状態の硬化物への変形（伸長回復率）が良好であることが求められる。
そして、今般、本発明者らは、特許第５２６７５７１号公報において開示される接着剤組成物の硬化物の伸長回復率にはさらなる改善の余地があるとの知見を得た。 Here, depending on the application, the adhesive composition is required to have good deformation (elongation recovery rate) from the stretched cured product to the cured product in the state before stretching.
The present inventors have now found that there is room for further improvement in the elongation recovery rate of the cured product of the adhesive composition disclosed in Japanese Patent No. 5267571.
そして、今般、本発明者らは、特許第５２６７５７１号公報において開示される接着剤組成物の硬化物の伸長回復率にはさらなる改善の余地があるとの知見を得た。 Here, depending on the application, the adhesive composition is required to have good deformation (elongation recovery rate) from the stretched cured product to the cured product in the state before stretching.
The present inventors have now found that there is room for further improvement in the elongation recovery rate of the cured product of the adhesive composition disclosed in Japanese Patent No. 5267571.
そして、本発明者らは、２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオールの２－シアノアクリレート化合物、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される少なくとも１種の化合物を含む、２－シアノアクリレート系接着剤組成物によれば、上記多官能シアノアクリレート化合物を含まない接着剤組成物に比べ、硬化物の伸長回復率が優れているとの知見を得た。
The present inventors have found that a cured product obtained by homopolymerizing a 2-cyanoacrylate compound has a storage elastic modulus at 25° C. of greater than 1.0×10 7 Pa and not more than 5.0×10 7 Pa, and the above Polyfunctional cyanoacrylate compounds include polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, 2-cyanoacrylate compounds of hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl formal , polyvinyl butyral, polyvinyl alcohol, phenolic resin, a silane compound having hydroxyl groups at both ends, and a siloxane compound having hydroxyl groups at both ends. The inventors have found that the cured product obtained from the adhesive composition has an excellent elongation recovery rate compared to the adhesive composition that does not contain the polyfunctional cyanoacrylate compound.
したがって、本開示の解決しようとする課題は、硬化物の伸長回復率に優れる２－シアノアクリレート系接着剤組成物を提供することである。
Therefore, the problem to be solved by the present disclosure is to provide a 2-cyanoacrylate-based adhesive composition that exhibits an excellent elongation recovery rate of the cured product.
上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞ ２－シアノアクリレート化合物と、多官能シアノアクリレート化合物とを含有し、上記２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む、２－シアノアクリレート系接着剤組成物。
＜２＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、１分経過したときの上記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）が５５％以上である、上記＜１＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１）
＜３＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、１分経過したときの上記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）をＬＡ、
伸長回復率ＬＡを測定した上記２－シアノアクリレート系接着剤組成物から上記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬａとしたとき、下記式（Ａ）を満たす、上記＜２＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１）
（ＬＡ－Ｌａ／Ｌａ）×１００≧５０％ （Ａ）
＜４＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、５分経過したときの上記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）が６５％以上である、上記＜１＞～＜３＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２）
＜５＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、５分経過したときの上記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）をＬＢ、
伸長回復率ＬＢを測定した上記２－シアノアクリレート系接着剤組成物から上記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬｂとしたとき、下記式（Ｂ）を満たす、上記＜４＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２）
（ＬＢ－Ｌｂ／Ｌｂ）×１００≧５０％ （Ｂ）
＜６＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、３０分経過したときの上記印間の長さ（Ｌ４）を測定し、下記計算式（３）から求められる伸長回復率（％）が７０％以上である、上記＜１＞～＜５＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ４）／（Ｌ１－Ｌ０）｝×１００ （３）
＜７＞ 上記２－シアノアクリレート化合物１００質量部に対し、上記多官能シアノアクリレート化合物を２質量部～５０質量部含有する、上記＜１＞～＜６＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜８＞ 上記２－シアノアクリレート化合物が、エーテル結合を有する、上記＜１＞～＜７＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜９＞ 上記２－シアノアクリレート化合物が、上記エーテル結合を２つ以上有する、上記＜８＞に記載の２－シアノアクリレート系接着剤組成物。
＜１０＞ 上記２－シアノアクリレート化合物が、下記式（１）で表される化合物を含む、上記＜１＞～＜９＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。 Means for solving the above problems include the following aspects.
<1> A cured product obtained by homopolymerizing the 2-cyanoacrylate compound and containing a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound has a storage modulus at 25° C. of 1.0×10 7 Pa or more. 5.0 × 10 7 Pa or less, and the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic 2-cyanoacrylic acid of a compound selected from the group consisting of polyols, polyurethane polyols, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resins, silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends A 2-cyanoacrylate adhesive composition containing at least one ester.
<2> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The 2-cyanoacrylate adhesive composition according to <1> above, wherein the length (L2) between the two is measured, and the elongation recovery rate (%) obtained from the following formula (1) is 55% or more.
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
<3> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The length between (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is LA,
When La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition obtained by excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured, the following is obtained. The 2-cyanoacrylate adhesive composition according to <2> above, which satisfies formula (A).
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
(LA−La/La)×100≧50% (A)
<4> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. 2. 2 according to any one of the above <1> to <3>, wherein the length (L3) is measured and the elongation recovery rate (%) obtained from the following formula (2) is 65% or more - Cyanoacrylate adhesive compositions.
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
<5> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. Measure the length (L3) between, and the elongation recovery rate (%) obtained from the following formula (2) is LB,
When the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb, the following is obtained. The 2-cyanoacrylate adhesive composition according to <4> above, which satisfies formula (B).
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
(LB-Lb/Lb)×100≧50% (B)
<6> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 30 minutes passed, the marking 2. 2 according to any one of the above <1> to <5>, wherein the length (L4) is measured and the elongation recovery rate (%) obtained from the following formula (3) is 70% or more - Cyanoacrylate adhesive compositions.
Elongation recovery rate (%): {(L1-L4) / (L1-L0)} × 100 (3)
<7> The 2- according to any one of the above <1> to <6>, which contains 2 parts by mass to 50 parts by mass of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound. A cyanoacrylate adhesive composition.
<8> The 2-cyanoacrylate adhesive composition according to any one of <1> to <7>, wherein the 2-cyanoacrylate compound has an ether bond.
<9> The 2-cyanoacrylate adhesive composition according to <8> above, wherein the 2-cyanoacrylate compound has two or more of the ether bonds.
<10> The 2-cyanoacrylate adhesive composition according to any one of <1> to <9> above, wherein the 2-cyanoacrylate compound contains a compound represented by the following formula (1).
＜１＞ ２－シアノアクリレート化合物と、多官能シアノアクリレート化合物とを含有し、上記２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む、２－シアノアクリレート系接着剤組成物。
＜２＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、１分経過したときの上記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）が５５％以上である、上記＜１＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１）
＜３＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、１分経過したときの上記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）をＬＡ、
伸長回復率ＬＡを測定した上記２－シアノアクリレート系接着剤組成物から上記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬａとしたとき、下記式（Ａ）を満たす、上記＜２＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１）
（ＬＡ－Ｌａ／Ｌａ）×１００≧５０％ （Ａ）
＜４＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、５分経過したときの上記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）が６５％以上である、上記＜１＞～＜３＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２）
＜５＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、５分経過したときの上記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）をＬＢ、
伸長回復率ＬＢを測定した上記２－シアノアクリレート系接着剤組成物から上記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬｂとしたとき、下記式（Ｂ）を満たす、上記＜４＞に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２）
（ＬＢ－Ｌｂ／Ｌｂ）×１００≧５０％ （Ｂ）
＜６＞ 上記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、上記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、上記治具の固定を解除し、３０分経過したときの上記印間の長さ（Ｌ４）を測定し、下記計算式（３）から求められる伸長回復率（％）が７０％以上である、上記＜１＞～＜５＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ４）／（Ｌ１－Ｌ０）｝×１００ （３）
＜７＞ 上記２－シアノアクリレート化合物１００質量部に対し、上記多官能シアノアクリレート化合物を２質量部～５０質量部含有する、上記＜１＞～＜６＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜８＞ 上記２－シアノアクリレート化合物が、エーテル結合を有する、上記＜１＞～＜７＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜９＞ 上記２－シアノアクリレート化合物が、上記エーテル結合を２つ以上有する、上記＜８＞に記載の２－シアノアクリレート系接着剤組成物。
＜１０＞ 上記２－シアノアクリレート化合物が、下記式（１）で表される化合物を含む、上記＜１＞～＜９＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。 Means for solving the above problems include the following aspects.
<1> A cured product obtained by homopolymerizing the 2-cyanoacrylate compound and containing a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound has a storage modulus at 25° C. of 1.0×10 7 Pa or more. 5.0 × 10 7 Pa or less, and the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic 2-cyanoacrylic acid of a compound selected from the group consisting of polyols, polyurethane polyols, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resins, silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends A 2-cyanoacrylate adhesive composition containing at least one ester.
<2> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The 2-cyanoacrylate adhesive composition according to <1> above, wherein the length (L2) between the two is measured, and the elongation recovery rate (%) obtained from the following formula (1) is 55% or more.
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
<3> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 1 minute passed, the marking The length between (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is LA,
When La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition obtained by excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured, the following is obtained. The 2-cyanoacrylate adhesive composition according to <2> above, which satisfies formula (A).
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
(LA−La/La)×100≧50% (A)
<4> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. 2. 2 according to any one of the above <1> to <3>, wherein the length (L3) is measured and the elongation recovery rate (%) obtained from the following formula (2) is 65% or more - Cyanoacrylate adhesive compositions.
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
<5> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 5 minutes, the mark was taken. Measure the length (L3) between, and the elongation recovery rate (%) obtained from the following formula (2) is LB,
When the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb, the following is obtained. The 2-cyanoacrylate adhesive composition according to <4> above, which satisfies formula (B).
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
(LB-Lb/Lb)×100≧50% (B)
<6> A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a distance between jigs of 20 mm (L0). After marking the jig fixing position and pulling at a tensile speed of 20 mm / min until the distance between the jigs became 40 mm (L1), the jig was released, and after 30 minutes passed, the marking 2. 2 according to any one of the above <1> to <5>, wherein the length (L4) is measured and the elongation recovery rate (%) obtained from the following formula (3) is 70% or more - Cyanoacrylate adhesive compositions.
Elongation recovery rate (%): {(L1-L4) / (L1-L0)} × 100 (3)
<7> The 2- according to any one of the above <1> to <6>, which contains 2 parts by mass to 50 parts by mass of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound. A cyanoacrylate adhesive composition.
<8> The 2-cyanoacrylate adhesive composition according to any one of <1> to <7>, wherein the 2-cyanoacrylate compound has an ether bond.
<9> The 2-cyanoacrylate adhesive composition according to <8> above, wherein the 2-cyanoacrylate compound has two or more of the ether bonds.
<10> The 2-cyanoacrylate adhesive composition according to any one of <1> to <9> above, wherein the 2-cyanoacrylate compound contains a compound represented by the following formula (1).
式（１）中、
Ｌ１はそれぞれ独立に、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－又は－ＣＨ２ＣＨ（Ｒ１）－を表し、
Ｒ１は置換基を有してもよい炭素数１～６の直鎖又は分岐のアルキル基を表し、
Ｒ２は置換基を有してもよい炭素数１～１５の直鎖又は分岐のアルキル基を表し、
ｐは１～５の整数を表す。
＜１１＞ 上記２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度が、８０℃以下である、上記＜１＞～＜１０＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜１２＞ 上記多官能シアノアクリレート化合物の数平均分子量が１，０００～５０，０００である、上記＜１＞～＜１１＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜１３＞ 上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオールの２－シアノアクリル酸エステルを含む、上記＜１＞～＜１２＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。 In formula (1),
L 1 each independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )-;
R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent;
R 2 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent;
p represents an integer of 1 to 5;
<11> Any of the above <1> to <10>, wherein the cured product obtained by homopolymerizing the 2-cyanoacrylate compound has a maximum loss tangent value (tan δ (max)) of 80°C or less. 2-cyanoacrylate adhesive composition according to any one of the above.
<12> The 2-cyanoacrylate adhesive composition according to any one of <1> to <11> above, wherein the polyfunctional cyanoacrylate compound has a number average molecular weight of 1,000 to 50,000.
<13> The 2-cyanoacrylate adhesive composition according to any one of <1> to <12> above, wherein the polyfunctional cyanoacrylate compound comprises a 2-cyanoacrylate ester of a polyoxyalkylene polyol. .
Ｌ１はそれぞれ独立に、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－又は－ＣＨ２ＣＨ（Ｒ１）－を表し、
Ｒ１は置換基を有してもよい炭素数１～６の直鎖又は分岐のアルキル基を表し、
Ｒ２は置換基を有してもよい炭素数１～１５の直鎖又は分岐のアルキル基を表し、
ｐは１～５の整数を表す。
＜１１＞ 上記２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度が、８０℃以下である、上記＜１＞～＜１０＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜１２＞ 上記多官能シアノアクリレート化合物の数平均分子量が１，０００～５０，０００である、上記＜１＞～＜１１＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。
＜１３＞ 上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオールの２－シアノアクリル酸エステルを含む、上記＜１＞～＜１２＞のいずれか１つに記載の２－シアノアクリレート系接着剤組成物。 In formula (1),
L 1 each independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )-;
R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent;
R 2 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent;
p represents an integer of 1 to 5;
<11> Any of the above <1> to <10>, wherein the cured product obtained by homopolymerizing the 2-cyanoacrylate compound has a maximum loss tangent value (tan δ (max)) of 80°C or less. 2-cyanoacrylate adhesive composition according to any one of the above.
<12> The 2-cyanoacrylate adhesive composition according to any one of <1> to <11> above, wherein the polyfunctional cyanoacrylate compound has a number average molecular weight of 1,000 to 50,000.
<13> The 2-cyanoacrylate adhesive composition according to any one of <1> to <12> above, wherein the polyfunctional cyanoacrylate compound comprises a 2-cyanoacrylate ester of a polyoxyalkylene polyol. .
本開示によれば、硬化物の伸長回復率に優れる２－シアノアクリレート系接着剤組成物を提供することができる。
According to the present disclosure, it is possible to provide a 2-cyanoacrylate-based adhesive composition that exhibits an excellent elongation recovery rate of the cured product.
以下、本開示を実施するための形態について詳細に説明する。但し、本開示は以下の実施形態に限定されない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示を制限するものではない。
A detailed description will be given below of the embodiment for implementing the present disclosure. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.
本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、合成例に示されている値に置き換えてもよい。
また、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。 In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . In addition, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
Moreover, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、合成例に示されている値に置き換えてもよい。
また、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。 In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . In addition, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
Moreover, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
（２－シアノアクリレート系接着剤組成物）
本開示の２－シアノアクリレート系接着剤組成物は、２－シアノアクリレート化合物と、多官能シアノアクリレート化合物とを含有し、上記２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む。 (2-cyanoacrylate adhesive composition)
The 2-cyanoacrylate-based adhesive composition of the present disclosure contains a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, and stores the cured product obtained by homopolymerizing the 2-cyanoacrylate compound at 25°C. The elastic modulus is greater than 1.0 × 10 7 Pa and 5.0 × 10 7 Pa or less, and the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, The group consisting of polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends at least one 2-cyanoacrylate ester of a compound selected from
本開示の２－シアノアクリレート系接着剤組成物は、２－シアノアクリレート化合物と、多官能シアノアクリレート化合物とを含有し、上記２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、上記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む。 (2-cyanoacrylate adhesive composition)
The 2-cyanoacrylate-based adhesive composition of the present disclosure contains a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, and stores the cured product obtained by homopolymerizing the 2-cyanoacrylate compound at 25°C. The elastic modulus is greater than 1.0 × 10 7 Pa and 5.0 × 10 7 Pa or less, and the polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, The group consisting of polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenolic resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends at least one 2-cyanoacrylate ester of a compound selected from
本発明者らが鋭意検討した結果、上記構成をとることにより、硬化物の伸長回復率に優れる２－シアノアクリレート系接着剤組成物を提供することができることを見出した。
これによる優れた効果の作用機構は明確ではないが、以下のように推定している。
２－シアノアクリレート系接着剤組成物が、単独重合させた硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下である２－シアノアクリレート化合物（以下、２－シアノアクリレート化合物を単独重合してなる硬化物を単独重合物ともいう）と、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む多官能シアノアクリレート化合物と、を組み合わせて含有させることにより、本開示の２－シアノアクリレート系接着剤組成物の硬化物（以下、単に、硬化物ともいう）のエントロピー弾性が向上することにより、硬化物の伸長前の状態への変形が促進され、硬化物の伸長回復率が向上すると推定される。 As a result of intensive studies by the present inventors, it was found that a 2-cyanoacrylate-based adhesive composition having an excellent elongation recovery rate of a cured product can be provided by adopting the above configuration.
Although the action mechanism of this excellent effect is not clear, it is presumed as follows.
The 2 - cyanoacrylate adhesive composition is a 2 - cyanoacrylate compound ( Hereinafter, a cured product obtained by homopolymerizing a 2-cyanoacrylate compound is also referred to as a homopolymer), polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated poly 2 of compounds selected from the group consisting of isoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends - A polyfunctional cyanoacrylate compound containing at least one cyanoacrylate ester in combination to obtain a cured product (hereinafter also simply referred to as a cured product) of the 2-cyanoacrylate adhesive composition of the present disclosure. It is presumed that the improvement in the entropy elasticity of the cured product accelerates the deformation to the state before elongation and improves the elongation recovery rate of the cured product.
これによる優れた効果の作用機構は明確ではないが、以下のように推定している。
２－シアノアクリレート系接着剤組成物が、単独重合させた硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下である２－シアノアクリレート化合物（以下、２－シアノアクリレート化合物を単独重合してなる硬化物を単独重合物ともいう）と、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む多官能シアノアクリレート化合物と、を組み合わせて含有させることにより、本開示の２－シアノアクリレート系接着剤組成物の硬化物（以下、単に、硬化物ともいう）のエントロピー弾性が向上することにより、硬化物の伸長前の状態への変形が促進され、硬化物の伸長回復率が向上すると推定される。 As a result of intensive studies by the present inventors, it was found that a 2-cyanoacrylate-based adhesive composition having an excellent elongation recovery rate of a cured product can be provided by adopting the above configuration.
Although the action mechanism of this excellent effect is not clear, it is presumed as follows.
The 2 - cyanoacrylate adhesive composition is a 2 - cyanoacrylate compound ( Hereinafter, a cured product obtained by homopolymerizing a 2-cyanoacrylate compound is also referred to as a homopolymer), polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated poly 2 of compounds selected from the group consisting of isoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends - A polyfunctional cyanoacrylate compound containing at least one cyanoacrylate ester in combination to obtain a cured product (hereinafter also simply referred to as a cured product) of the 2-cyanoacrylate adhesive composition of the present disclosure. It is presumed that the improvement in the entropy elasticity of the cured product accelerates the deformation to the state before elongation and improves the elongation recovery rate of the cured product.
＜２－シアノアクリレート化合物＞
本開示の２－シアノアクリレート系接着剤組成物は、単独重合させた硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下である２－シアノアクリレート化合物（以下、特定２－シアノアクリレート化合物ともいう。）を含有する。
なお、本開示の２－シアノアクリレート系接着剤組成物は、特定２－シアノアクリレート化合物を２種以上含有していてもよい。 <2-cyanoacrylate compound>
The 2-cyanoacrylate adhesive composition of the present disclosure has a storage modulus at 25° C. of a cured product obtained by homopolymerization of 2-cyanoacrylate having a storage modulus of more than 1.0×10 7 Pa and not more than 5.0×10 7 Pa. Contains an acrylate compound (hereinafter also referred to as a specific 2-cyanoacrylate compound).
The 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds.
本開示の２－シアノアクリレート系接着剤組成物は、単独重合させた硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下である２－シアノアクリレート化合物（以下、特定２－シアノアクリレート化合物ともいう。）を含有する。
なお、本開示の２－シアノアクリレート系接着剤組成物は、特定２－シアノアクリレート化合物を２種以上含有していてもよい。 <2-cyanoacrylate compound>
The 2-cyanoacrylate adhesive composition of the present disclosure has a storage modulus at 25° C. of a cured product obtained by homopolymerization of 2-cyanoacrylate having a storage modulus of more than 1.0×10 7 Pa and not more than 5.0×10 7 Pa. Contains an acrylate compound (hereinafter also referred to as a specific 2-cyanoacrylate compound).
The 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds.
硬化物の伸長回復率の観点から、単独重合物の２５℃における貯蔵弾性率は、１．１×１０７Ｐａ～４．０×１０７Ｐａであることが好ましく、１．２×１０７Ｐａ～３．０×１０７Ｐａであることがより好ましい。
From the viewpoint of the elongation recovery rate of the cured product, the storage elastic modulus of the homopolymer at 25° C. is preferably 1.1×10 7 Pa to 4.0×10 7 Pa, more preferably 1.2×10 7 Pa. It is more preferably ~3.0×10 7 Pa.
本開示において、特定２－シアノアクリレート化合物を単独重合してなる硬化物の貯蔵弾性率の測定は下記の通り行う。
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定する。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とする。
次いで、上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分、相対湿度５０％の条件で、－５０℃～１５０℃の範囲において、ずりによる硬化物の貯蔵弾性率を測定し、２５℃における硬化物の貯蔵弾性率を求める。
なお、動的粘弾性測定装置としては、アントンパール社製のＭＣＲ３０１又はこれと同程度の装置を使用することができる。 In the present disclosure, the storage modulus of a cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound is measured as follows.
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using the dynamic viscoelasticity measuring device, the storage elasticity was measured under the conditions of a frequency of 1 Hz, a temperature of 25 ° C., and a thickness of 300 μm. measure the rate.
After confirming that the storage modulus of the 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the 2-cyanoacrylate compound.
Next, using the cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz, a temperature increase rate of 2 ° C./min, and a relative humidity of 50%. Determine the storage elastic modulus of the cured product at °C.
As the dynamic viscoelasticity measuring device, MCR301 manufactured by Anton Paar or a similar device can be used.
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定する。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とする。
次いで、上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分、相対湿度５０％の条件で、－５０℃～１５０℃の範囲において、ずりによる硬化物の貯蔵弾性率を測定し、２５℃における硬化物の貯蔵弾性率を求める。
なお、動的粘弾性測定装置としては、アントンパール社製のＭＣＲ３０１又はこれと同程度の装置を使用することができる。 In the present disclosure, the storage modulus of a cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound is measured as follows.
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using the dynamic viscoelasticity measuring device, the storage elasticity was measured under the conditions of a frequency of 1 Hz, a temperature of 25 ° C., and a thickness of 300 μm. measure the rate.
After confirming that the storage modulus of the 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the 2-cyanoacrylate compound.
Next, using the cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz, a temperature increase rate of 2 ° C./min, and a relative humidity of 50%. Determine the storage elastic modulus of the cured product at °C.
As the dynamic viscoelasticity measuring device, MCR301 manufactured by Anton Paar or a similar device can be used.
硬化物の伸長回復率の観点から、特定２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度は、８０℃以下であることが好ましく、７７℃以下であることがより好ましい。
上記温度の下限値は特に限定されるものではないが、例えば、５０℃以上とすることができる。 From the viewpoint of the elongation recovery rate of the cured product, the temperature at which the cured product obtained by homopolymerizing the specific 2-cyanoacrylate compound shows the maximum loss tangent value (tan δ (max)) is preferably 80° C. or less. It is more preferably 77° C. or lower.
Although the lower limit of the temperature is not particularly limited, it can be, for example, 50° C. or higher.
上記温度の下限値は特に限定されるものではないが、例えば、５０℃以上とすることができる。 From the viewpoint of the elongation recovery rate of the cured product, the temperature at which the cured product obtained by homopolymerizing the specific 2-cyanoacrylate compound shows the maximum loss tangent value (tan δ (max)) is preferably 80° C. or less. It is more preferably 77° C. or lower.
Although the lower limit of the temperature is not particularly limited, it can be, for example, 50° C. or higher.
本開示において、特定２－シアノアクリレート化合物の損失正接の極大値を示す温度の測定は下記の通り行う。
特定２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定する。
特定２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを特定２－シアノアクリレート化合物の硬化物とする。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分の条件で、－５０℃～１５０℃の範囲において、動的粘弾性スペクトルを求め、損失正接（ｔａｎδ）が最大値となる温度を測定する。ピークが２つ以上観察される場合、最も大きいピークとなる損失正接（ｔａｎδ）を極大値とする。
なお、使用することができる動的粘弾性測定装置は、上記した通りである。 In the present disclosure, the temperature at which the loss tangent of a specific 2-cyanoacrylate compound exhibits a maximum value is measured as follows.
After injecting the specific 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, the dynamic viscoelasticity measuring device was used to store the compound under the conditions of a frequency of 1 Hz, a temperature of 25°C, and a thickness of 300 µm. Measure the elastic modulus.
After confirming that the storage modulus of the specific 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the specific 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz and a temperature increase rate of 2 ° C./min, and determine the temperature at which the loss tangent (tan δ) becomes the maximum value. Measure. When two or more peaks are observed, the maximum loss tangent (tan δ) is taken as the maximum value.
In addition, the dynamic viscoelasticity measuring device that can be used is as described above.
特定２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定する。
特定２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを特定２－シアノアクリレート化合物の硬化物とする。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分の条件で、－５０℃～１５０℃の範囲において、動的粘弾性スペクトルを求め、損失正接（ｔａｎδ）が最大値となる温度を測定する。ピークが２つ以上観察される場合、最も大きいピークとなる損失正接（ｔａｎδ）を極大値とする。
なお、使用することができる動的粘弾性測定装置は、上記した通りである。 In the present disclosure, the temperature at which the loss tangent of a specific 2-cyanoacrylate compound exhibits a maximum value is measured as follows.
After injecting the specific 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, the dynamic viscoelasticity measuring device was used to store the compound under the conditions of a frequency of 1 Hz, a temperature of 25°C, and a thickness of 300 µm. Measure the elastic modulus.
After confirming that the storage modulus of the specific 2-cyanoacrylate compound no longer changes, this is defined as a cured product of the specific 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz and a temperature increase rate of 2 ° C./min, and determine the temperature at which the loss tangent (tan δ) becomes the maximum value. Measure. When two or more peaks are observed, the maximum loss tangent (tan δ) is taken as the maximum value.
In addition, the dynamic viscoelasticity measuring device that can be used is as described above.
硬化物の伸長回復率の観点から、特定２－シアノアクリレート化合物は、エーテル結合を有することが好ましい。また、同様の観点から、特定２－シアノアクリレート化合物は、エーテル結合を２個以上有することが好ましく、２個～５個有することがより好ましく、２個～４個有することがさらに好ましく、２個又は３個有することが特に好ましい。
なお、本開示の２－シアノアクリレート系接着剤組成物は、エーテル結合の数が異なる特定２－シアノアクリレート化合物を２種以上含有していてもよい。 The specific 2-cyanoacrylate compound preferably has an ether bond from the viewpoint of the elongation recovery rate of the cured product. Further, from the same viewpoint, the specific 2-cyanoacrylate compound preferably has 2 or more ether bonds, more preferably 2 to 5, even more preferably 2 to 4, and 2 Or it is particularly preferable to have three.
The 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds having different numbers of ether bonds.
なお、本開示の２－シアノアクリレート系接着剤組成物は、エーテル結合の数が異なる特定２－シアノアクリレート化合物を２種以上含有していてもよい。 The specific 2-cyanoacrylate compound preferably has an ether bond from the viewpoint of the elongation recovery rate of the cured product. Further, from the same viewpoint, the specific 2-cyanoacrylate compound preferably has 2 or more ether bonds, more preferably 2 to 5, even more preferably 2 to 4, and 2 Or it is particularly preferable to have three.
The 2-cyanoacrylate adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds having different numbers of ether bonds.
硬化物の伸長回復率の観点から、特定２－シアノアクリレート化合物は、下記式（１）で表される化合物を含むことが好ましい。
From the viewpoint of the elongation recovery rate of the cured product, the specific 2-cyanoacrylate compound preferably contains a compound represented by the following formula (1).
式（１）中、Ｌ１はそれぞれ独立に、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－又は－ＣＨ２ＣＨ（Ｒ１）－を表し、硬化物の伸長回復率の観点からは、－ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－又は－ＣＨ２ＣＨ（Ｒ１）－であることが好ましく、－ＣＨ２ＣＨ２－であることがより好ましい。
In formula (1), each L 1 independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- , -CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )- is preferable from the viewpoint of the elongation recovery rate of the cured product, and -CH 2 CH 2 - is more preferable.
式（１）中、Ｒ１は置換基を有してもよい炭素数１～６、好ましくは炭素数１～３のアルキル基を表し、また、直鎖アルキル基であっても、分岐アルキル基であってもよい。上記置換基としては、アリール基、ハロゲン原子、アルコキシ基、アリーロキシ基、シアノ基、アルコキシカルボニル基、アリーロキシカルボニル基、アシル基、アシルオキシ基が挙げられる。Ｒ１としては、例えば、メチル基、エチル基、プロピル基等が挙げられ、硬化物の伸長回復率の観点からは、メチル基又はエチル基が好ましく、エチル基がより好ましい。
In formula (1), R 1 represents an optionally substituted alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. may be Examples of the substituents include aryl groups, halogen atoms, alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, and acyloxy groups. Examples of R 1 include a methyl group, an ethyl group, a propyl group, and the like, and from the viewpoint of the elongation recovery rate of the cured product, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
式（１）中、Ｒ２は置換基を有していてもよい炭素数１～１５のアルキル基を表し、また、直鎖アルキル基であっても、分岐アルキル基であってもよい。上記置換基としては、Ｒ１において前述した置換基が挙げられる。
式（１）におけるＲ２は、硬化物の伸長回復率の観点から、炭素数３～１５のアルキル基であることが好ましく、４～１３のアルキル基であることがより好ましく、炭素数４～１０のアルキル基であることがさらに好ましい。
式（１）におけるＲ２としては、２－エチルへキシル基、２－メチルへキシル基、２－エチルブチル基、２－メチルブチル基、２－メチルペンチル基、２－エチルペンチル基、２－メチルヘプチル基、１－メチルペンチル基、１－エチルペンチル基、１－プロピルペンチル基、１－メチルヘキシル基、１－エチルヘキシル基、１－メチルヘプチル基、１－メチルブチル基、１－エチルプロピル基、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等が挙げられ、硬化物の伸長回復率の観点から、２－エチルへキシル基又はｎ－ブチル基が好ましい。 In formula (1), R 2 represents an optionally substituted alkyl group having 1 to 15 carbon atoms, and may be a linear alkyl group or a branched alkyl group. Examples of the substituent include the substituents described above for R 1 .
R 2 in formula (1) is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 4 to 13 carbon atoms, from the viewpoint of the elongation recovery rate of the cured product, and more preferably an alkyl group having 4 to 13 carbon atoms. 10 alkyl groups are more preferred.
R 2 in formula (1) includes 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group and 2-methylheptyl. group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group , ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. A 2-ethylhexyl group or an n-butyl group is preferable from the viewpoint of the elongation recovery rate of the product.
式（１）におけるＲ２は、硬化物の伸長回復率の観点から、炭素数３～１５のアルキル基であることが好ましく、４～１３のアルキル基であることがより好ましく、炭素数４～１０のアルキル基であることがさらに好ましい。
式（１）におけるＲ２としては、２－エチルへキシル基、２－メチルへキシル基、２－エチルブチル基、２－メチルブチル基、２－メチルペンチル基、２－エチルペンチル基、２－メチルヘプチル基、１－メチルペンチル基、１－エチルペンチル基、１－プロピルペンチル基、１－メチルヘキシル基、１－エチルヘキシル基、１－メチルヘプチル基、１－メチルブチル基、１－エチルプロピル基、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等が挙げられ、硬化物の伸長回復率の観点から、２－エチルへキシル基又はｎ－ブチル基が好ましい。 In formula (1), R 2 represents an optionally substituted alkyl group having 1 to 15 carbon atoms, and may be a linear alkyl group or a branched alkyl group. Examples of the substituent include the substituents described above for R 1 .
R 2 in formula (1) is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 4 to 13 carbon atoms, from the viewpoint of the elongation recovery rate of the cured product, and more preferably an alkyl group having 4 to 13 carbon atoms. 10 alkyl groups are more preferred.
R 2 in formula (1) includes 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group and 2-methylheptyl. group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group , ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. A 2-ethylhexyl group or an n-butyl group is preferable from the viewpoint of the elongation recovery rate of the product.
式（１）中、ｐは１～５の整数を表し、硬化物の伸長回復率の観点からは、１～４の整数であることが好ましく、１～３の整数であることがより好ましく、２であることがさらに好ましい。
In formula (1), p represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, from the viewpoint of the elongation recovery rate of the cured product, 2 is more preferred.
式（１）中、ｐが１又は２であり、且つＬ１が－ＣＨ２ＣＨ２－である場合、硬化物の伸長回復率の観点からは、Ｒ２は２－エチルへキシル基、２－メチルへキシル基、２－エチルブチル基、２－メチルブチル基、２－メチルペンチル基、２－メチルヘプチル基、２－エチルペンチル基、１－メチルペンチル基、１－エチルペンチル基、１－プロピルペンチル基、１－メチルヘキシル基、１－エチルヘキシル基、１－メチルヘプチル基、１－メチルブチル基、１－エチルプロピル基、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基又はｎ－オクチル基が好ましく、２－エチルへキシル基又は２－メチルへキシル基であることがより好ましく、２－エチルへキシル基であることがさらに好ましい。
In formula (1), when p is 1 or 2 and L 1 is —CH 2 CH 2 —, from the viewpoint of the elongation recovery rate of the cured product, R 2 is a 2-ethylhexyl group, 2 -methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-methylheptyl group, 2-ethylpentyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group or n-octyl group is preferable, 2-ethylhexyl group or 2-methylhexyl group is more preferable, -Ethylhexyl group is more preferred.
式（１）中、ｐが１であり、且つＬ１が－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－若しくは－ＣＨ２ＣＨ（Ｒ１）－の場合、硬化物の伸長回復率の観点からは、Ｒ２は２－エチルへキシル基、２－メチルへキシル基、２－エチルブチル基、２－メチルブチル基、２－メチルペンチル基、２－エチルペンチル基、２－メチルヘプチル基、１－メチルペンチル基、１－エチルペンチル基、１－プロピルペンチル基、１－メチルヘキシル基、１－エチルヘキシル基、１－メチルヘプチル基、１－メチルブチル基、１－エチルプロピル基、
メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基であることが好ましく、２－エチルへキシル基、２－メチルへキシル基又はｎ－ブチル基であることがより好ましく、２－エチルへキシル基又はｎ－ブチル基であることがさらに好ましい。 In formula (1), when p is 1 and L 1 is —CH 2 CH 2 CH 2 —, —CH(R 1 )CH 2 — or —CH 2 CH(R 1 )—, the cured product From the standpoint of elongation recovery rate, R 2 is 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-methyl heptyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group,
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group A 2-ethylhexyl group, a 2-methylhexyl group or an n-butyl group is preferred, and a 2-ethylhexyl group or an n-butyl group is even more preferred.
メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基であることが好ましく、２－エチルへキシル基、２－メチルへキシル基又はｎ－ブチル基であることがより好ましく、２－エチルへキシル基又はｎ－ブチル基であることがさらに好ましい。 In formula (1), when p is 1 and L 1 is —CH 2 CH 2 CH 2 —, —CH(R 1 )CH 2 — or —CH 2 CH(R 1 )—, the cured product From the standpoint of elongation recovery rate, R 2 is 2-ethylhexyl group, 2-methylhexyl group, 2-ethylbutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-methyl heptyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-methylheptyl group, 1-methylbutyl group, 1-ethylpropyl group,
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group A 2-ethylhexyl group, a 2-methylhexyl group or an n-butyl group is preferred, and a 2-ethylhexyl group or an n-butyl group is even more preferred.
式（１）で表される化合物の具体例としては、２－（２－エチルヘキシルオキシ）エチル、２－（２－ブトキシエトキシ）エチル、２－（１－メチルブトキシ）エチル、２－（２－エチルブトキシ）エチル、２－（２－メチルブトキシ）エチル、２－ペンチルオキシエチル、２－（２－メチルペンチルオキシ）エチル、２－（２－エチルペンチルオキシ）エチル、２－（２－メチルヘキシルオキシ）エチル、２－（２－メチルヘプチルオキシ）エチル、２－ヘキシルオキシエチル、２－（１－メチルペンチルオキシ）エチル、２－ヘプチルオキシエチル、２－（１－メチルヘキシルオキシ）エチル、２－（１エチルペンチルオキシ）エチル、２－オクチルオキシエチル、２－（１－メチルヘプチルオキシ）エチル、２－（１－エチルヘキシルオキシ）エチル、２－（１－プロピルペンチルオキシ）エチル、２－［２－（２－エチルヘキシルオキシ）エトキシ］エチル、２－［２－（２－ブトキシエトキシ）エトキシ］エチル、２－［２－（２－エチルブトキシ）エトキシ］エチル、２－［２－（２－メチルブトキシ）エトキシ］エチル、２－（２－ペンチルオキシエトキシ）エチル、２－［２－（１－メチルブトキシ）エトキシ］エチル、２－［２－（２－メチルペンチルオキシ）エトキシ］エチル、２－［２－（２－エチルペンチルオキシ）エトキシ］エチル、２－［２－（２－メチルヘキシルオキシ）エトキシ］エチル、２－［２－（２－メチルヘプチルオキシ）エトキシ］エチル、２－（２－ヘキシルオキシエトキシ）エチル、２－［２－（１―メチルペンチルオキシ）エトキシ］エチル、２－（２－ヘプチルオキシエトキシ）エチル、２－［２－（１－メチルヘキシルオキシ）エトキシ］エチル、２－［２－（１－エチルペンチルオキシ）エトキシ］エチル、２－（２－オクチルオキシエトキシ）エチル、２－［２－（１－メチルヘプチルオキシ）エトキシ］エチル、２－［２－（１－エチルヘプチルオキシ）エトキシ］エチル、２－［２－（１－プロピルペンチルオキシ）エトキシ］エチル、１－（２－エチルヘキシルオキシ）プロピル－２－イル、２－（２－エチルヘキシルオキシ）プロピル－１－イル、１－メトキシプロピル－２－イル、２－メトキシプロピル－１－イル、１－エトキシプロピル－２－イル、２－エトキシプロピル－１－イル、１－プロポキシプロピル－２－イル、２－プロポキシプロピル－１－イル、１－（１－メチルエトキシ）プロピル－２－イル、２－（１－メチルエトキシ）プロピル－１－イル、１－ブトキシプロピル－２－イル、２－ブトキシプロピル－１－イル、１－（２－メチルプロポキシ）プロピル－２－イル、２－（２－メチルプロポキシ）プロピル－１－イル、１－（２－エチルブトキシ）プロピル－２－イル、２－（２－エチルブトキシ）プロピル－１－イル、１－（１－メチルプロポキシ）プロピル－２－イル、２－（１－メチルプロポキシ）プロピル－１－イル、１－（２－メチルブトキシ）プロピル－２－イル、２－（２－メチルブトキシ）プロピル－１－イル、１－ペンチルオキシプロピル－２－イル、２－ペンチルオキシプロピル－１－イル、１－（１－メチルブトキシ）プロピル－２－イル、２－（１－メチルブトキシ）プロピル－１－イル、１－（１－エチルプロポキシ）プロピル－２－イル、２－（１－エチルプロポキシ）プロピル－１－イル、１－（２－メチルペンチルオキシ）プロピル－２－イル、２－（２－メチルペンチルオキシ）プロピル－１－イル、１－（２－エチルペンチルオキシ）プロピル－２－イル、２－（２－エチルペンチルオキシ）プロピル－１－イル、１－（２－メチルヘキシルオキシ）プロピル－２－イル、２－（２－メチルヘキシルオキシ）プロピル－１－イル、１－（２－メチルヘプチルオキシ）プロピル－２－イル、２－（２－メチルヘプチルオキシ）プロピル－１－イル、１－ヘキシルオキシプロピル－２－イル、２－ヘキシルオキシプロピル－１－イル、１－（１－メチルペンチルオキシ）プロピル－２－イル、２－（１－メチルペンチルオキシ）プロピル－１－イル、１－ヘプチルオキシプロピル－２－イル、２－ヘプチルオキシプロピル－１－イル、１－（１－メチルヘキシルオキシ）プロピル－２－イル、２－（１－メチルヘキシルオキシ）プロピル－１－イル、１－（１－エチルペンチルオキシ）プロピル－２－イル、２－（１－エチルペンチルオキシ）プロピル－１－イル、１－オクチルオキシプロピル－２－イル、２－オクチルオキシプロピル－１－イル、１－（１－メチルヘプチルオキシ）プロピル－２－イル、２－（１－メチルヘプチルオキシ）プロピル－１－イル、１－（１－エチルヘキシルオキシ）プロピル－２－イル、２－（１－エチルヘキシルオキシ）プロピル－１－イル、１－（１－プロピルペンチルオキシ）プロピル－２－イル、２－（１－プロピルペンチルオキシ）プロピル－１－イル等の２－シアノアクリル酸エステルが挙げられる。
上記した中でも、硬化物の伸長回復率の観点から、２－（２－エチルヘキシルオキシ）エチル－２－シアノアクリレート、２－［２－（２－エチルヘキシルオキシ）エトキシ］エチル－２－シアノアクリレート又は２－（２－ブトキシエトキシ）エチル－２－シアノアクリレートが好ましく、２－［２－（２－エチルヘキシルオキシ）エトキシ］エチル－２－シアノアクリレート又は２－（２－ブトキシエトキシ）エチル－２－シアノアクリレートの２－シアノアクリル酸エステルがより好ましい。 Specific examples of the compound represented by formula (1) include 2-(2-ethylhexyloxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-(1-methylbutoxy)ethyl, 2-(2- Ethylbutoxy)ethyl, 2-(2-methylbutoxy)ethyl, 2-pentyloxyethyl, 2-(2-methylpentyloxy)ethyl, 2-(2-ethylpentyloxy)ethyl, 2-(2-methylhexyl oxy)ethyl, 2-(2-methylheptyloxy)ethyl, 2-hexyloxyethyl, 2-(1-methylpentyloxy)ethyl, 2-heptyloxyethyl, 2-(1-methylhexyloxy)ethyl, 2 -(1-ethylpentyloxy)ethyl, 2-octyloxyethyl, 2-(1-methylheptyloxy)ethyl, 2-(1-ethylhexyloxy)ethyl, 2-(1-propylpentyloxy)ethyl, 2-[ 2-(2-ethylhexyloxy)ethoxy]ethyl, 2-[2-(2-butoxyethoxy)ethoxy]ethyl, 2-[2-(2-ethylbutoxy)ethoxy]ethyl, 2-[2-(2- methylbutoxy)ethoxy]ethyl, 2-(2-pentyloxyethoxy)ethyl, 2-[2-(1-methylbutoxy)ethoxy]ethyl, 2-[2-(2-methylpentyloxy)ethoxy]ethyl, 2 -[2-(2-ethylpentyloxy)ethoxy]ethyl, 2-[2-(2-methylhexyloxy)ethoxy]ethyl, 2-[2-(2-methylheptyloxy)ethoxy]ethyl, 2-( 2-hexyloxyethoxy)ethyl, 2-[2-(1-methylpentyloxy)ethoxy]ethyl, 2-(2-heptyloxyethoxy)ethyl, 2-[2-(1-methylhexyloxy)ethoxy]ethyl , 2-[2-(1-ethylpentyloxy)ethoxy]ethyl, 2-(2-octyloxyethoxy)ethyl, 2-[2-(1-methylheptyloxy)ethoxy]ethyl, 2-[2-( 1-ethylheptyloxy)ethoxy]ethyl, 2-[2-(1-propylpentyloxy)ethoxy]ethyl, 1-(2-ethylhexyloxy)propyl-2-yl, 2-(2-ethylhexyloxy)propyl- 1-yl, 1-methoxypropyl-2-yl, 2-methoxypropyl-1-yl, 1-ethoxypropyl-2-yl, 2-ethoxypropyl-1-yl, 1-propoxypropyl-2-yl, 2 - Propoxypropyl -1-yl, 1-(1-methylethoxy)propyl-2-yl, 2-(1-methylethoxy)propyl-1-yl, 1-butoxypropyl-2-yl, 2-butoxypropyl-1-yl , 1-(2-methylpropoxy)propyl-2-yl, 2-(2-methylpropoxy)propyl-1-yl, 1-(2-ethylbutoxy)propyl-2-yl, 2-(2-ethylbutoxy ) propyl-1-yl, 1-(1-methylpropoxy)propyl-2-yl, 2-(1-methylpropoxy)propyl-1-yl, 1-(2-methylbutoxy)propyl-2-yl, 2 -(2-methylbutoxy)propyl-1-yl, 1-pentyloxypropyl-2-yl, 2-pentyloxypropyl-1-yl, 1-(1-methylbutoxy)propyl-2-yl, 2-( 1-methylbutoxy)propyl-1-yl, 1-(1-ethylpropoxy)propyl-2-yl, 2-(1-ethylpropoxy)propyl-1-yl, 1-(2-methylpentyloxy)propyl- 2-yl, 2-(2-methylpentyloxy)propyl-1-yl, 1-(2-ethylpentyloxy)propyl-2-yl, 2-(2-ethylpentyloxy)propyl-1-yl, 1 -(2-methylhexyloxy)propyl-2-yl, 2-(2-methylhexyloxy)propyl-1-yl, 1-(2-methylheptyloxy)propyl-2-yl, 2-(2-methyl Heptyloxy)propyl-1-yl, 1-hexyloxypropyl-2-yl, 2-hexyloxypropyl-1-yl, 1-(1-methylpentyloxy)propyl-2-yl, 2-(1-methyl Pentyloxy)propyl-1-yl, 1-heptyloxypropyl-2-yl, 2-heptyloxypropyl-1-yl, 1-(1-methylhexyloxy)propyl-2-yl, 2-(1-methyl Hexyloxy)propyl-1-yl, 1-(1-ethylpentyloxy)propyl-2-yl, 2-(1-ethylpentyloxy)propyl-1-yl, 1-octyloxypropyl-2-yl, 2 -octyloxypropyl-1-yl, 1-(1-methylheptyloxy)propyl-2-yl, 2-(1-methylheptyloxy)propyl-1-yl, 1-(1-ethylhexyloxy)propyl-2 -yl, 2-(1-ethylhexyloxy)propyl-1-yl, 1-(1-propylpentyloxy) 2-cyanoacrylates such as oxy)propyl-2-yl and 2-(1-propylpentyloxy)propyl-1-yl.
Among the above, from the viewpoint of the elongation recovery rate of the cured product, 2-(2-ethylhexyloxy)ethyl-2-cyanoacrylate, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2 -(2-butoxyethoxy)ethyl-2-cyanoacrylate is preferred, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2-(2-butoxyethoxy)ethyl-2-cyanoacrylate 2-cyanoacrylate esters of are more preferred.
上記した中でも、硬化物の伸長回復率の観点から、２－（２－エチルヘキシルオキシ）エチル－２－シアノアクリレート、２－［２－（２－エチルヘキシルオキシ）エトキシ］エチル－２－シアノアクリレート又は２－（２－ブトキシエトキシ）エチル－２－シアノアクリレートが好ましく、２－［２－（２－エチルヘキシルオキシ）エトキシ］エチル－２－シアノアクリレート又は２－（２－ブトキシエトキシ）エチル－２－シアノアクリレートの２－シアノアクリル酸エステルがより好ましい。 Specific examples of the compound represented by formula (1) include 2-(2-ethylhexyloxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-(1-methylbutoxy)ethyl, 2-(2- Ethylbutoxy)ethyl, 2-(2-methylbutoxy)ethyl, 2-pentyloxyethyl, 2-(2-methylpentyloxy)ethyl, 2-(2-ethylpentyloxy)ethyl, 2-(2-methylhexyl oxy)ethyl, 2-(2-methylheptyloxy)ethyl, 2-hexyloxyethyl, 2-(1-methylpentyloxy)ethyl, 2-heptyloxyethyl, 2-(1-methylhexyloxy)ethyl, 2 -(1-ethylpentyloxy)ethyl, 2-octyloxyethyl, 2-(1-methylheptyloxy)ethyl, 2-(1-ethylhexyloxy)ethyl, 2-(1-propylpentyloxy)ethyl, 2-[ 2-(2-ethylhexyloxy)ethoxy]ethyl, 2-[2-(2-butoxyethoxy)ethoxy]ethyl, 2-[2-(2-ethylbutoxy)ethoxy]ethyl, 2-[2-(2- methylbutoxy)ethoxy]ethyl, 2-(2-pentyloxyethoxy)ethyl, 2-[2-(1-methylbutoxy)ethoxy]ethyl, 2-[2-(2-methylpentyloxy)ethoxy]ethyl, 2 -[2-(2-ethylpentyloxy)ethoxy]ethyl, 2-[2-(2-methylhexyloxy)ethoxy]ethyl, 2-[2-(2-methylheptyloxy)ethoxy]ethyl, 2-( 2-hexyloxyethoxy)ethyl, 2-[2-(1-methylpentyloxy)ethoxy]ethyl, 2-(2-heptyloxyethoxy)ethyl, 2-[2-(1-methylhexyloxy)ethoxy]ethyl , 2-[2-(1-ethylpentyloxy)ethoxy]ethyl, 2-(2-octyloxyethoxy)ethyl, 2-[2-(1-methylheptyloxy)ethoxy]ethyl, 2-[2-( 1-ethylheptyloxy)ethoxy]ethyl, 2-[2-(1-propylpentyloxy)ethoxy]ethyl, 1-(2-ethylhexyloxy)propyl-2-yl, 2-(2-ethylhexyloxy)propyl- 1-yl, 1-methoxypropyl-2-yl, 2-methoxypropyl-1-yl, 1-ethoxypropyl-2-yl, 2-ethoxypropyl-1-yl, 1-propoxypropyl-2-yl, 2 - Propoxypropyl -1-yl, 1-(1-methylethoxy)propyl-2-yl, 2-(1-methylethoxy)propyl-1-yl, 1-butoxypropyl-2-yl, 2-butoxypropyl-1-yl , 1-(2-methylpropoxy)propyl-2-yl, 2-(2-methylpropoxy)propyl-1-yl, 1-(2-ethylbutoxy)propyl-2-yl, 2-(2-ethylbutoxy ) propyl-1-yl, 1-(1-methylpropoxy)propyl-2-yl, 2-(1-methylpropoxy)propyl-1-yl, 1-(2-methylbutoxy)propyl-2-yl, 2 -(2-methylbutoxy)propyl-1-yl, 1-pentyloxypropyl-2-yl, 2-pentyloxypropyl-1-yl, 1-(1-methylbutoxy)propyl-2-yl, 2-( 1-methylbutoxy)propyl-1-yl, 1-(1-ethylpropoxy)propyl-2-yl, 2-(1-ethylpropoxy)propyl-1-yl, 1-(2-methylpentyloxy)propyl- 2-yl, 2-(2-methylpentyloxy)propyl-1-yl, 1-(2-ethylpentyloxy)propyl-2-yl, 2-(2-ethylpentyloxy)propyl-1-yl, 1 -(2-methylhexyloxy)propyl-2-yl, 2-(2-methylhexyloxy)propyl-1-yl, 1-(2-methylheptyloxy)propyl-2-yl, 2-(2-methyl Heptyloxy)propyl-1-yl, 1-hexyloxypropyl-2-yl, 2-hexyloxypropyl-1-yl, 1-(1-methylpentyloxy)propyl-2-yl, 2-(1-methyl Pentyloxy)propyl-1-yl, 1-heptyloxypropyl-2-yl, 2-heptyloxypropyl-1-yl, 1-(1-methylhexyloxy)propyl-2-yl, 2-(1-methyl Hexyloxy)propyl-1-yl, 1-(1-ethylpentyloxy)propyl-2-yl, 2-(1-ethylpentyloxy)propyl-1-yl, 1-octyloxypropyl-2-yl, 2 -octyloxypropyl-1-yl, 1-(1-methylheptyloxy)propyl-2-yl, 2-(1-methylheptyloxy)propyl-1-yl, 1-(1-ethylhexyloxy)propyl-2 -yl, 2-(1-ethylhexyloxy)propyl-1-yl, 1-(1-propylpentyloxy) 2-cyanoacrylates such as oxy)propyl-2-yl and 2-(1-propylpentyloxy)propyl-1-yl.
Among the above, from the viewpoint of the elongation recovery rate of the cured product, 2-(2-ethylhexyloxy)ethyl-2-cyanoacrylate, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2 -(2-butoxyethoxy)ethyl-2-cyanoacrylate is preferred, 2-[2-(2-ethylhexyloxy)ethoxy]ethyl-2-cyanoacrylate or 2-(2-butoxyethoxy)ethyl-2-cyanoacrylate 2-cyanoacrylate esters of are more preferred.
硬化物の伸長回復率の観点から、２－シアノアクリレート系接着剤組成物１００質量部に対する特定２－シアノアクリレート化合物の含有量は、５０質量部以上であることが好ましく、６０質量部以上であることがより好ましく、７０質量部以上であることがさらに好ましく、７５質量部以上であることが特に好ましく、８０質量部以上であることが最も好ましい。
特定２－シアノアクリレート化合物の含有量の上限値は、特に限定されるものではないが、例えば、９０質量部以下とすることができる。 From the viewpoint of the elongation recovery rate of the cured product, the content of the specific 2-cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate adhesive composition is preferably 50 parts by mass or more, and is 60 parts by mass or more. more preferably 70 parts by mass or more, particularly preferably 75 parts by mass or more, and most preferably 80 parts by mass or more.
The upper limit of the content of the specific 2-cyanoacrylate compound is not particularly limited, but can be, for example, 90 parts by mass or less.
特定２－シアノアクリレート化合物の含有量の上限値は、特に限定されるものではないが、例えば、９０質量部以下とすることができる。 From the viewpoint of the elongation recovery rate of the cured product, the content of the specific 2-cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate adhesive composition is preferably 50 parts by mass or more, and is 60 parts by mass or more. more preferably 70 parts by mass or more, particularly preferably 75 parts by mass or more, and most preferably 80 parts by mass or more.
The upper limit of the content of the specific 2-cyanoacrylate compound is not particularly limited, but can be, for example, 90 parts by mass or less.
特定２－シアノアクリレート化合物が、式（１）で表される化合物を含む場合、硬化物の伸長回復率の観点から、２－シアノアクリレート系接着剤組成物に含有される特定２－シアノアクリレート化合物１００質量部に対する式（１）で表される化合物の含有量は、７０質量部以上であることが好ましく、８０質量部以上であることがより好ましく、９０質量部以上であることがさらに好ましく、９５質量部以上であることが特に好ましく、１００質量部であってもよい。
When the specific 2-cyanoacrylate compound contains the compound represented by formula (1), the specific 2-cyanoacrylate compound contained in the 2-cyanoacrylate-based adhesive composition from the viewpoint of the elongation recovery rate of the cured product. The content of the compound represented by formula (1) with respect to 100 parts by mass is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, It is particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
＜多官能シアノアクリレート化合物＞
本開示の２－シアノアクリレート系接着剤組成物は、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む、多官能シアノアクリレート化合物を含有する。
上記した中でも、硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物は、ポリオキシアルキレンポリオール及びアクリルポリオールからなる群より選択される化合物の２－シアノアクリル酸エステルを含むことが好ましく、ポリオキシアルキレンポリオールの２－シアノアクリル酸エステルを含むことがより好ましい。
なお、本開示において、多官能シアノアクリレート化合物とは、２個以上のシアノアクリロイル基を有する化合物を意味する。 <Polyfunctional cyanoacrylate compound>
The 2-cyanoacrylate adhesive composition of the present disclosure includes polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl Formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, at least one 2-cyanoacrylic acid ester of a compound selected from the group consisting of silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends. , contains a polyfunctional cyanoacrylate compound.
Among the above, from the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains a 2-cyanoacrylate ester of a compound selected from the group consisting of polyoxyalkylene polyols and acrylic polyols. More preferably, it contains a 2-cyanoacrylate ester of an oxyalkylene polyol.
In addition, in this disclosure, the polyfunctional cyanoacrylate compound means a compound having two or more cyanoacryloyl groups.
本開示の２－シアノアクリレート系接着剤組成物は、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む、多官能シアノアクリレート化合物を含有する。
上記した中でも、硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物は、ポリオキシアルキレンポリオール及びアクリルポリオールからなる群より選択される化合物の２－シアノアクリル酸エステルを含むことが好ましく、ポリオキシアルキレンポリオールの２－シアノアクリル酸エステルを含むことがより好ましい。
なお、本開示において、多官能シアノアクリレート化合物とは、２個以上のシアノアクリロイル基を有する化合物を意味する。 <Polyfunctional cyanoacrylate compound>
The 2-cyanoacrylate adhesive composition of the present disclosure includes polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, acrylic polyols, polyurethane polyols, polyvinyl Formal, polyvinyl butyral, polyvinyl alcohol, phenol resin, at least one 2-cyanoacrylic acid ester of a compound selected from the group consisting of silane compounds having hydroxyl groups at both ends and siloxane compounds having hydroxyl groups at both ends. , contains a polyfunctional cyanoacrylate compound.
Among the above, from the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains a 2-cyanoacrylate ester of a compound selected from the group consisting of polyoxyalkylene polyols and acrylic polyols. More preferably, it contains a 2-cyanoacrylate ester of an oxyalkylene polyol.
In addition, in this disclosure, the polyfunctional cyanoacrylate compound means a compound having two or more cyanoacryloyl groups.
ポリオキシアルキレンポリオールとしては、特に限定されるものではないが、ポリオキシエチレングリコール、ポリオキシエチレントリオール、ポリオキシエチレンテトラオール、ポリオキシプロピレングリコール、ポリオキシプロピレントリオール、ポリオキシプロピレンテトラオール、ポリオキシテトラメチレングリコール等、及びポリオール或いは他のグリコールとの共重合体などを用いることができる。
また、ポリエステルポリオールとしては、特に限定されるものではないが、アジピン酸等の二塩基酸とグリコール、トリオール等との反応により生成する一般的なポリエステルポリオール、カプロラクトンを開環重合させたポリカプロラクトンポリオールなどを用いることができる。
また、ポリカーボネートポリオールとしては、特に限定されるものではないが、エチレンカーボネート等から誘導される一般的なポリカーボネートジオール、カーボネートとグリコールとを共重合させたものなどを用いることができる。
また、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオールの２－シアノアクリル酸エステルは、硬化物の柔軟性及び強靭性に加えて、耐温水性の観点からも好ましい。 The polyoxyalkylene polyol is not particularly limited, but includes polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, polyoxy Tetramethylene glycol, etc., and copolymers with polyols or other glycols, etc. can be used.
In addition, the polyester polyol is not particularly limited, but general polyester polyol produced by reaction of dibasic acid such as adipic acid with glycol, triol, etc., polycaprolactone polyol obtained by ring-opening polymerization of caprolactone. etc. can be used.
The polycarbonate polyol is not particularly limited, but a general polycarbonate diol derived from ethylene carbonate or the like, a copolymer of carbonate and glycol, and the like can be used.
Polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and 2-cyanoacrylate of hydrogenated polyisoprene polyol are preferable from the viewpoint of hot water resistance in addition to the flexibility and toughness of the cured product.
また、ポリエステルポリオールとしては、特に限定されるものではないが、アジピン酸等の二塩基酸とグリコール、トリオール等との反応により生成する一般的なポリエステルポリオール、カプロラクトンを開環重合させたポリカプロラクトンポリオールなどを用いることができる。
また、ポリカーボネートポリオールとしては、特に限定されるものではないが、エチレンカーボネート等から誘導される一般的なポリカーボネートジオール、カーボネートとグリコールとを共重合させたものなどを用いることができる。
また、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオールの２－シアノアクリル酸エステルは、硬化物の柔軟性及び強靭性に加えて、耐温水性の観点からも好ましい。 The polyoxyalkylene polyol is not particularly limited, but includes polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, polyoxy Tetramethylene glycol, etc., and copolymers with polyols or other glycols, etc. can be used.
In addition, the polyester polyol is not particularly limited, but general polyester polyol produced by reaction of dibasic acid such as adipic acid with glycol, triol, etc., polycaprolactone polyol obtained by ring-opening polymerization of caprolactone. etc. can be used.
The polycarbonate polyol is not particularly limited, but a general polycarbonate diol derived from ethylene carbonate or the like, a copolymer of carbonate and glycol, and the like can be used.
Polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and 2-cyanoacrylate of hydrogenated polyisoprene polyol are preferable from the viewpoint of hot water resistance in addition to the flexibility and toughness of the cured product.
硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物は、官能基数２～１２であるシアノアクリル酸エステルを含むことが好ましく、官能基数２～６であるシアノアクリル酸エステルを含むことがより好ましく、官能基数２～４であるシアノアクリル酸エステルを含むことがさらに好ましく、官能基数２又は３であるシアノアクリル酸エステル（ビスシアノアクリレート化合物又はトリスシアノアクリレート化合物）を含むことが特に好ましい。
硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物は、ビスシアノアクリル酸エステル及びトリスシアノアクリル酸エステルの少なくとも一方を含むことが好ましい。
硬化物の伸長回復率の観点から、ビスシアノアクリル酸エステルは、ポリオキシアルキレンポリオールビスシアノアクリル酸エステル又はアルカンジオールビスシアノアクリル酸エステルであることが好ましい。
硬化物の伸長回復率の観点から、トリスシアノアクリル酸エステルは、ポリオキシアルキレンポリオールトリシアノアクリル酸エステルであることが好ましい。
ポリオキシアルキレンポリオールビスシアノアクリレート化合物又はポリオキシアルキレンポリオールトリシアノアクリル酸エステルを構成する、ポリオキシアルキレンポリオールとしては、ポリオキシプロピレングリコール（ＰＰＧ）、ポリオキシエチレングリコール、ポリオキシテトラメチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール、ポリオキシプロピレンポリオキシテトラメチレングリコール等が挙げられる。
上記した中でも、硬化物の伸長回復率の観点から、ポリオキシプロピレングリコール（ＰＰＧ）－ビスシアノアクリレート又はポリオキシプロピレングリコール（ＰＰＧ）－トリスシアノアクリレートが好ましい。
アルカンジオールビスシアノアクリル酸エステルとしては、１，６－ヘキサンジオール－ビスシアノアクリレート、１，４－ブタンジオール－ビスシアノアクリレート、１，８－オクタンジオール－ビスシアノアクリレート、１，９－ノナンジオール－ビスシアノアクリレート、１，１０－デカンジオール－ビスシアノアクリレート、１，１２－ドデカンジオール－ビスシアノアクリレート等が挙げられる。 From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains a cyanoacrylate ester having 2 to 12 functional groups, and more preferably contains a cyanoacrylate ester having 2 to 6 functional groups. It preferably contains a cyanoacrylate having 2 to 4 functional groups, and particularly preferably contains a cyanoacrylate having 2 or 3 functional groups (bis-cyanoacrylate compound or tris-cyanoacrylate compound).
From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains at least one of biscyanoacrylate and triscyanoacrylate.
From the viewpoint of the elongation recovery rate of the cured product, the biscyanoacrylate is preferably a polyoxyalkylene polyol biscyanoacrylate or an alkanediol biscyanoacrylate.
From the viewpoint of the elongation recovery rate of the cured product, the triscyanoacrylate is preferably a polyoxyalkylene polyol tricyanoacrylate.
Polyoxyalkylene polyols constituting the polyoxyalkylene polyol biscyanoacrylate compound or polyoxyalkylene polyol tricyanoacrylate include polyoxypropylene glycol (PPG), polyoxyethylene glycol, polyoxytetramethylene glycol, polyoxy Examples include ethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol and the like.
Among them, polyoxypropylene glycol (PPG)-biscyanoacrylate or polyoxypropylene glycol (PPG)-triscyanoacrylate is preferable from the viewpoint of elongation recovery rate of the cured product.
Examples of alkanediol biscyanoacrylates include 1,6-hexanediol-biscyanoacrylate, 1,4-butanediol-biscyanoacrylate, 1,8-octanediol-biscyanoacrylate, 1,9-nonanediol- biscyanoacrylate, 1,10-decanediol-biscyanoacrylate, 1,12-dodecanediol-biscyanoacrylate and the like.
硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物は、ビスシアノアクリル酸エステル及びトリスシアノアクリル酸エステルの少なくとも一方を含むことが好ましい。
硬化物の伸長回復率の観点から、ビスシアノアクリル酸エステルは、ポリオキシアルキレンポリオールビスシアノアクリル酸エステル又はアルカンジオールビスシアノアクリル酸エステルであることが好ましい。
硬化物の伸長回復率の観点から、トリスシアノアクリル酸エステルは、ポリオキシアルキレンポリオールトリシアノアクリル酸エステルであることが好ましい。
ポリオキシアルキレンポリオールビスシアノアクリレート化合物又はポリオキシアルキレンポリオールトリシアノアクリル酸エステルを構成する、ポリオキシアルキレンポリオールとしては、ポリオキシプロピレングリコール（ＰＰＧ）、ポリオキシエチレングリコール、ポリオキシテトラメチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール、ポリオキシプロピレンポリオキシテトラメチレングリコール等が挙げられる。
上記した中でも、硬化物の伸長回復率の観点から、ポリオキシプロピレングリコール（ＰＰＧ）－ビスシアノアクリレート又はポリオキシプロピレングリコール（ＰＰＧ）－トリスシアノアクリレートが好ましい。
アルカンジオールビスシアノアクリル酸エステルとしては、１，６－ヘキサンジオール－ビスシアノアクリレート、１，４－ブタンジオール－ビスシアノアクリレート、１，８－オクタンジオール－ビスシアノアクリレート、１，９－ノナンジオール－ビスシアノアクリレート、１，１０－デカンジオール－ビスシアノアクリレート、１，１２－ドデカンジオール－ビスシアノアクリレート等が挙げられる。 From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains a cyanoacrylate ester having 2 to 12 functional groups, and more preferably contains a cyanoacrylate ester having 2 to 6 functional groups. It preferably contains a cyanoacrylate having 2 to 4 functional groups, and particularly preferably contains a cyanoacrylate having 2 or 3 functional groups (bis-cyanoacrylate compound or tris-cyanoacrylate compound).
From the viewpoint of the elongation recovery rate of the cured product, the polyfunctional cyanoacrylate compound preferably contains at least one of biscyanoacrylate and triscyanoacrylate.
From the viewpoint of the elongation recovery rate of the cured product, the biscyanoacrylate is preferably a polyoxyalkylene polyol biscyanoacrylate or an alkanediol biscyanoacrylate.
From the viewpoint of the elongation recovery rate of the cured product, the triscyanoacrylate is preferably a polyoxyalkylene polyol tricyanoacrylate.
Polyoxyalkylene polyols constituting the polyoxyalkylene polyol biscyanoacrylate compound or polyoxyalkylene polyol tricyanoacrylate include polyoxypropylene glycol (PPG), polyoxyethylene glycol, polyoxytetramethylene glycol, polyoxy Examples include ethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol and the like.
Among them, polyoxypropylene glycol (PPG)-biscyanoacrylate or polyoxypropylene glycol (PPG)-triscyanoacrylate is preferable from the viewpoint of elongation recovery rate of the cured product.
Examples of alkanediol biscyanoacrylates include 1,6-hexanediol-biscyanoacrylate, 1,4-butanediol-biscyanoacrylate, 1,8-octanediol-biscyanoacrylate, 1,9-nonanediol- biscyanoacrylate, 1,10-decanediol-biscyanoacrylate, 1,12-dodecanediol-biscyanoacrylate and the like.
硬化物の伸長回復率の観点から、多官能シアノアクリレート化合物の分子量又は数平均分子量（Ｍｎ）は、１，０００～５０，０００であることが好ましく、１，０００～１０，０００であることがより好ましく、１，０００～５，０００であることがさらに好ましい。
なお、本開示において、Ｍｎは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて得られた標準ポリスチレン換算値である。 From the viewpoint of the elongation recovery rate of the cured product, the molecular weight or number average molecular weight (Mn) of the polyfunctional cyanoacrylate compound is preferably 1,000 to 50,000, more preferably 1,000 to 10,000. It is more preferably 1,000 to 5,000.
In addition, in this indication, Mn is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
なお、本開示において、Ｍｎは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて得られた標準ポリスチレン換算値である。 From the viewpoint of the elongation recovery rate of the cured product, the molecular weight or number average molecular weight (Mn) of the polyfunctional cyanoacrylate compound is preferably 1,000 to 50,000, more preferably 1,000 to 10,000. It is more preferably 1,000 to 5,000.
In addition, in this indication, Mn is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
硬化物の伸長回復率の観点から、本開示の２－シアノアクリレート系接着剤組成物に含有される２－シアノアクリレート化合物１００質量部に対する多官能シアノアクリレート化合物の含有量は、２質量部～５０質量部であることが好ましく、７質量部～３０質量部であることがより好ましく、１０質量部～２０質量部であることがさらに好ましく、１３質量部～１８質量部であることが特に好ましく、１４質量部～１７質量部であることが最も好ましい。
From the viewpoint of the elongation recovery rate of the cured product, the content of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure is 2 parts by mass to 50 parts by mass. It is preferably 7 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 20 parts by mass, and particularly preferably 13 parts by mass to 18 parts by mass. 14 parts by mass to 17 parts by mass is most preferred.
硬化物の伸長回復率の観点から、２－シアノアクリレート系接着剤組成物に含有される多官能シアノアクリレート１００質量部に対するポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール及び水添ポリイソプレンポリオールからなる群より選択される化合物の２－シアノアクリレート化合物の含有量の和は、７０質量部以上であることが好ましく、８０質量部以上であることがより好ましく、９０質量部以上であることがさらに好ましく、９５質量部以上であることが特に好ましく、１００質量部であってもよい。
From the viewpoint of the elongation recovery rate of the cured product, polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, relative to 100 parts by mass of polyfunctional cyanoacrylate contained in the 2-cyanoacrylate adhesive composition, The sum of the contents of the 2-cyanoacrylate compounds in the compounds selected from the group consisting of polyisoprene polyols and hydrogenated polyisoprene polyols is preferably 70 parts by mass or more, more preferably 80 parts by mass or more. , more preferably 90 parts by mass or more, particularly preferably 95 parts by mass or more, and may be 100 parts by mass.
＜その他の成分＞
本開示の２－シアノアクリレート系接着剤組成物は、その特性を損なわない範囲において、特定２－シアノアクリレート化合物及び多官能シアノアクリレート化合物以外のその他の成分を含有していてもよい。
その他の成分としては、特定２－シアノアクリレート化合物以外の２－シアノアクリレート化合物、安定剤、硬化促進剤、可塑剤、増粘剤、粒子、着色剤、香料、溶剤、強度向上剤等が挙げられる。 <Other ingredients>
The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain components other than the specific 2-cyanoacrylate compound and the polyfunctional cyanoacrylate compound within a range that does not impair its properties.
Other components include 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds, stabilizers, curing accelerators, plasticizers, thickeners, particles, colorants, fragrances, solvents, strength improvers, and the like. .
本開示の２－シアノアクリレート系接着剤組成物は、その特性を損なわない範囲において、特定２－シアノアクリレート化合物及び多官能シアノアクリレート化合物以外のその他の成分を含有していてもよい。
その他の成分としては、特定２－シアノアクリレート化合物以外の２－シアノアクリレート化合物、安定剤、硬化促進剤、可塑剤、増粘剤、粒子、着色剤、香料、溶剤、強度向上剤等が挙げられる。 <Other ingredients>
The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain components other than the specific 2-cyanoacrylate compound and the polyfunctional cyanoacrylate compound within a range that does not impair its properties.
Other components include 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds, stabilizers, curing accelerators, plasticizers, thickeners, particles, colorants, fragrances, solvents, strength improvers, and the like. .
特定２－シアノアクリレート化合物以外の２－シアノアクリレート化合物としては、２－シアノアクリル酸のメチル、エチル、クロロエチル、ｎ－プロピル、ｉ－プロピル、アリル、プロパギル、ｎ－ブチル、ｉ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、シクロヘキシル、フェニル、テトラヒドロフルフリル、ヘプチル、２－エチルヘキシル、ｎ－オクチル、２－オクチル、ｎ－ノニル、オキソノニル、ｎ－デシル、ｎ－ドデシル、メトキシエチル、メトキシプロピル、メトキシイソプロピル、メトキシブチル、エトキシエチル、エトキシプロピル、エトキシイソプロピル、プロポキシメチル、プロポキシエチル、イソプロポキシエチル、プロポキシプロピル、ブトキシメチル、ブトキシエチル、ブトキシプロピル、ブトキシイソプロピル、ブトキシブチル、２，２，２－トリフルオロエチル、ヘキサフルオロイソプロピル等のエステルが挙げられる。これらの２－シアノアクリレート化合物は１種のみ用いてもよく、２種以上を併用してもよい。
Examples of 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n- Pentyl, n-hexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl, 2-ethylhexyl, n-octyl, 2-octyl, n-nonyl, oxononyl, n-decyl, n-dodecyl, methoxyethyl, methoxypropyl, methoxyisopropyl , methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxyisopropyl, propoxymethyl, propoxyethyl, isopropoxyethyl, propoxypropyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxyisopropyl, butoxybutyl, 2,2,2-trifluoroethyl , hexafluoroisopropyl and the like. These 2-cyanoacrylate compounds may be used alone or in combination of two or more.
安定剤としては、（１）二酸化硫黄及びメタンスルホン酸等の脂肪族スルホン酸、ｐ－トルエンスルホン酸等の芳香族スルホン酸、三弗化ホウ素メタノール、三弗化ホウ素ジエチルエーテル等の三弗化ホウ素錯体、ＨＢＦ４、トリアルキルボレート等のアニオン重合禁止剤、（２）ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ－ブチルカテコール、カテコール、ピロガロール等のラジカル重合禁止剤などが挙げられる。これらの安定剤は１種のみ用いてもよく、２種以上を併用してもよい。
Stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and trifluorides such as boron trifluoride methanol and boron trifluoride diethyl ether. Examples include boron complexes, anionic polymerization inhibitors such as HBF 4 and trialkylborate, and radical polymerization inhibitors such as (2) hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol and pyrogallol. These stabilizers may be used alone or in combination of two or more.
硬化促進剤としては、２－シアノアクリレート系接着剤組成物のアニオン重合を促進するものであれば、いずれも使用することができる。硬化促進剤としては、ポリエーテル化合物、カリックスアレン類、チアカリックスアレン類、ピロガロールアレン類、オニウム塩等が挙げられる。これらの硬化促進剤は１種のみ用いてもよく、２種以上を併用してもよい。
Any curing accelerator can be used as long as it accelerates the anionic polymerization of the 2-cyanoacrylate adhesive composition. Curing accelerators include polyether compounds, calixarenes, thiacalixarenes, pyrogallolarenes, onium salts and the like. One of these curing accelerators may be used alone, or two or more thereof may be used in combination.
また、可塑剤としては、アセチルクエン酸トリエチル、アセチルクエン酸トリブチル、アジピン酸ジメチル、アジピン酸ジエチル、セバシン酸ジメチル、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジイソデシル、フタル酸ジヘキシル、フタル酸ジヘプチル、フタル酸ジオクチル、フタル酸ビス（２－エチルヘキシル）、フタル酸ジイソノニル、フタル酸ジイソトリデシル、フタル酸ジペンタデシル、テレフタル酸ジオクチル、イソフタル酸ジイソノニル、トルイル酸デシル、ショウノウ酸ビス（２－エチルヘキシル）、２－エチルヘキシルシクロヘキシルカルボキシレート、フマル酸ジイソブチル、マレイン酸ジイソブチル、カプロン酸トリグリセライド、安息香酸２－エチルヘキシル、ジプロピレングリコールジベンゾエート等が挙げられる。これらの中では、２－シアノアクリレート化合物との相溶性がよく、かつ可塑化効率が高いという点から、アセチルクエン酸トリブチル、アジピン酸ジメチル、フタル酸ジメチル、安息香酸２－エチルヘキシル又はジプロピレングリコールジベンゾエートが好ましい。これらの可塑剤は１種のみ用いてもよく、２種以上を併用してもよい。
Plasticizers include acetyl triethyl citrate, acetyl tributyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and phthalate. diheptyl acid, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl) camphorate, 2 -ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, caproic acid triglyceride, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate and the like. Among these, acetyl tributyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate or dipropylene glycol dipropylene glycol are preferred because of their good compatibility with 2-cyanoacrylate compounds and high plasticization efficiency. Benzoates are preferred. These plasticizers may be used alone or in combination of two or more.
増粘剤としては、ポリメタクリル酸メチル、メタクリル酸メチルとアクリル酸エステルとの共重合体、メタクリル酸メチルとその他のメタクリル酸エステルとの共重合体、アクリルゴム、ポリ酢酸ビニル、ポリ塩化ビニル、ポリウレタン樹脂、ポリアミド樹脂、ポリスチレン、セルロースエステル、ポリアルキル－２－シアノアクリル酸エステル、エチレン－酢酸ビニル共重合体等が挙げられる。これらの増粘剤は１種のみ用いてもよく、２種以上を併用してもよい。
Examples of thickeners include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic acid esters, copolymers of methyl methacrylate and other methacrylic acid esters, acrylic rubber, polyvinyl acetate, polyvinyl chloride, Polyurethane resins, polyamide resins, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylic acid esters, ethylene-vinyl acetate copolymers, and the like. These thickeners may be used alone or in combination of two or more.
本開示の２－シアノアクリレート系接着剤組成物は、その特性を損なわない範囲において、粒子を含んでいてもよく、これにより、２－シアノアクリレート系接着剤組成物を使用することにより形成される接着剤層の厚さを調整することができる。
粒子の平均粒子径は、１０μｍ～２００μｍであることが好ましく、１５μｍ～２００μｍであることがより好ましく、１５μｍ～１５０μｍであることが更に好ましい。
粒子の材質は、使用する２－シアノアクリレート化合物等に不溶であり、且つ重合等の変質を引き起こさないものであれば特に限定されない。粒子としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン、アクリル樹脂、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスルホン、ポリフェニレンオキサイド等の熱可塑性樹脂；不飽和ポリエステル、ジビニルベンゼン重合体、ジビニルベンゼン－スチレン共重合体、ジビニルベンゼン－（メタ）アクリル酸エステル共重合体、ジアリルフタレート重合体等の架橋樹脂；球状シリカ、ガラスビーズ、ガラスファイバー等の無機化合物；シリコーン化合物；有機ポリマー骨格とポリシロキサン骨格を含んでなる有機無機複合粒子等が挙げられる。
また、粒子の含有量は特に限定されないが、硬化速度、接着強さ等の観点からは、本開示の２－シアノアクリレート系接着剤組成物に含有される２－シアノアクリレート化合物１００質量に対する粒子の含有量は、０．１質量部～１０質量部であることが好ましく、１質量部～５質量部であることがより好ましく、１質量部～３質量部であることが更に好ましい。
なお、本開示において、粒子の平均粒子径は、レーザー回折式粒度分布測定装置によって測定した体積基準の平均値である。 The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain particles to the extent that the properties thereof are not impaired, and are thus formed by using the 2-cyanoacrylate-based adhesive composition. The thickness of the adhesive layer can be adjusted.
The average particle diameter of the particles is preferably 10 μm to 200 μm, more preferably 15 μm to 200 μm, even more preferably 15 μm to 150 μm.
The material of the particles is not particularly limited as long as it is insoluble in the 2-cyanoacrylate compound or the like used and does not cause deterioration such as polymerization. Particles include thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, and polyphenylene oxide; unsaturated polyesters, divinylbenzene polymers, Crosslinked resins such as divinylbenzene-styrene copolymers, divinylbenzene-(meth)acrylate copolymers, and diallyl phthalate polymers; inorganic compounds such as spherical silica, glass beads, and glass fibers; silicone compounds; Examples include organic-inorganic composite particles containing a polysiloxane skeleton.
The content of the particles is not particularly limited, but from the viewpoint of curing speed, adhesive strength, etc., the amount of particles per 100 mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure. The content is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, even more preferably 1 to 3 parts by mass.
In addition, in the present disclosure, the average particle diameter of particles is a volume-based average value measured by a laser diffraction particle size distribution analyzer.
粒子の平均粒子径は、１０μｍ～２００μｍであることが好ましく、１５μｍ～２００μｍであることがより好ましく、１５μｍ～１５０μｍであることが更に好ましい。
粒子の材質は、使用する２－シアノアクリレート化合物等に不溶であり、且つ重合等の変質を引き起こさないものであれば特に限定されない。粒子としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン、アクリル樹脂、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスルホン、ポリフェニレンオキサイド等の熱可塑性樹脂；不飽和ポリエステル、ジビニルベンゼン重合体、ジビニルベンゼン－スチレン共重合体、ジビニルベンゼン－（メタ）アクリル酸エステル共重合体、ジアリルフタレート重合体等の架橋樹脂；球状シリカ、ガラスビーズ、ガラスファイバー等の無機化合物；シリコーン化合物；有機ポリマー骨格とポリシロキサン骨格を含んでなる有機無機複合粒子等が挙げられる。
また、粒子の含有量は特に限定されないが、硬化速度、接着強さ等の観点からは、本開示の２－シアノアクリレート系接着剤組成物に含有される２－シアノアクリレート化合物１００質量に対する粒子の含有量は、０．１質量部～１０質量部であることが好ましく、１質量部～５質量部であることがより好ましく、１質量部～３質量部であることが更に好ましい。
なお、本開示において、粒子の平均粒子径は、レーザー回折式粒度分布測定装置によって測定した体積基準の平均値である。 The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain particles to the extent that the properties thereof are not impaired, and are thus formed by using the 2-cyanoacrylate-based adhesive composition. The thickness of the adhesive layer can be adjusted.
The average particle diameter of the particles is preferably 10 μm to 200 μm, more preferably 15 μm to 200 μm, even more preferably 15 μm to 150 μm.
The material of the particles is not particularly limited as long as it is insoluble in the 2-cyanoacrylate compound or the like used and does not cause deterioration such as polymerization. Particles include thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, acrylic resins, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, and polyphenylene oxide; unsaturated polyesters, divinylbenzene polymers, Crosslinked resins such as divinylbenzene-styrene copolymers, divinylbenzene-(meth)acrylate copolymers, and diallyl phthalate polymers; inorganic compounds such as spherical silica, glass beads, and glass fibers; silicone compounds; Examples include organic-inorganic composite particles containing a polysiloxane skeleton.
The content of the particles is not particularly limited, but from the viewpoint of curing speed, adhesive strength, etc., the amount of particles per 100 mass of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure. The content is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, even more preferably 1 to 3 parts by mass.
In addition, in the present disclosure, the average particle diameter of particles is a volume-based average value measured by a laser diffraction particle size distribution analyzer.
＜本開示の２－シアノアクリレート系接着剤組成物の硬化物の伸長回復率＞
上記した本開示の２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、治具の固定を解除し、１分経過したときの印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）は、５５％以上であることが好ましく、５８％以上であることがより好ましく、６０％以上であることがさらに好ましく、６３％以上であることが特に好ましい。
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１） <Elongation recovery rate of the cured product of the 2-cyanoacrylate adhesive composition of the present disclosure>
A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after one minute has passed The length (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is preferably 55% or more, more preferably 58% or more, and 60% or more. is more preferable, and 63% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
上記した本開示の２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、治具の固定を解除し、１分経過したときの印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）は、５５％以上であることが好ましく、５８％以上であることがより好ましく、６０％以上であることがさらに好ましく、６３％以上であることが特に好ましい。
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１） <Elongation recovery rate of the cured product of the 2-cyanoacrylate adhesive composition of the present disclosure>
A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after one minute has passed The length (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is preferably 55% or more, more preferably 58% or more, and 60% or more. is more preferable, and 63% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
上記した本開示の２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、治具の固定を解除し、５分経過したときの印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）は、６５％以上であることが好ましく、６７％以上であることがより好ましく、７０％以上であることがさらに好ましく、７５％以上であることが特に好ましい。
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 5 minutes The length (L3) is measured, and the elongation recovery rate (%) obtained from the following formula (2) is preferably 65% or more, more preferably 67% or more, and 70% or more. is more preferable, and 75% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 5 minutes The length (L3) is measured, and the elongation recovery rate (%) obtained from the following formula (2) is preferably 65% or more, more preferably 67% or more, and 70% or more. is more preferable, and 75% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
上記した本開示の２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、治具の固定を解除し、３０分経過したときの印間の長さ（Ｌ４）を測定し、下記計算式（３）から求められる伸長回復率（％）は、７０％以上であることが好ましく、７３％以上であることがより好ましく、７５％以上であることがさらに好ましく、８０％以上であることが特に好ましい。
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ４）／（Ｌ１－Ｌ０）｝×１００ （３） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 30 minutes The length (L4) is measured, and the elongation recovery rate (%) obtained from the following formula (3) is preferably 70% or more, more preferably 73% or more, and 75% or more. is more preferable, and 80% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L4) / (L1-L0)} × 100 (3)
なお、伸長回復率の測定は、温度２５℃、相対湿度５０％の環境において行う。
伸長回復率（％）：｛（Ｌ１－Ｌ４）／（Ｌ１－Ｌ０）｝×１００ （３） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition of the present disclosure is fixed to a tensile tester with a jig distance of 20 mm (L0), Mark the jig fixing position, pull at a tensile speed of 20 mm / min until the distance between the jigs is 40 mm (L1), then release the jig fixation, and after 30 minutes The length (L4) is measured, and the elongation recovery rate (%) obtained from the following formula (3) is preferably 70% or more, more preferably 73% or more, and 75% or more. is more preferable, and 80% or more is particularly preferable.
The elongation recovery rate is measured in an environment of 25° C. temperature and 50% relative humidity.
Elongation recovery rate (%): {(L1-L4) / (L1-L0)} × 100 (3)
なお、上記伸長回復率の測定に使用される引張試験機としては、株式会社東洋精機製作所のストログラフＶ２０－Ｃ又はこれと同程度の装置を使用することができる。
また、上記伸長回復率の測定に使用される硬化物は、下記のようにして製造する。
まず、離型ポリエチレンテレフタレート（ＰＥＴ）フィルム上に、厚さ１ｍｍのシリコーンゴムの型枠を配置する。
次いで、本開示の２－シアノアクリレート系接着剤組成物１ｇに、トリエタノールアミンを１μＬ添加し、撹拌した後、上記型枠内へ流し込む。
２－シアノアクリレート系接着剤組成物の流し込み後、型枠及び接着剤組成物上に、別途用意した上記離型ＰＥＴフィルムを被せ、ガラス板で挟み込んだ後、温度２５℃、相対湿度５０％で２４時間静置し、完全に硬化させる。
硬化後、型枠及び離型ＰＥＴフィルムを取り除いて、幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を得る。 As a tensile tester used for measuring the elongation recovery rate, a Strograph V20-C manufactured by Toyo Seiki Seisakusho Co., Ltd. or a similar device can be used.
Moreover, the cured product used for the measurement of the elongation recovery rate is produced as follows.
First, a silicone rubber mold with a thickness of 1 mm is placed on a release polyethylene terephthalate (PET) film.
Next, 1 μL of triethanolamine is added to 1 g of the 2-cyanoacrylate-based adhesive composition of the present disclosure, stirred, and poured into the mold.
After pouring the 2-cyanoacrylate adhesive composition, the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and then at a temperature of 25 ° C. and a relative humidity of 50%. Allow 24 hours to fully cure.
After curing, the mold and release PET film are removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
また、上記伸長回復率の測定に使用される硬化物は、下記のようにして製造する。
まず、離型ポリエチレンテレフタレート（ＰＥＴ）フィルム上に、厚さ１ｍｍのシリコーンゴムの型枠を配置する。
次いで、本開示の２－シアノアクリレート系接着剤組成物１ｇに、トリエタノールアミンを１μＬ添加し、撹拌した後、上記型枠内へ流し込む。
２－シアノアクリレート系接着剤組成物の流し込み後、型枠及び接着剤組成物上に、別途用意した上記離型ＰＥＴフィルムを被せ、ガラス板で挟み込んだ後、温度２５℃、相対湿度５０％で２４時間静置し、完全に硬化させる。
硬化後、型枠及び離型ＰＥＴフィルムを取り除いて、幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を得る。 As a tensile tester used for measuring the elongation recovery rate, a Strograph V20-C manufactured by Toyo Seiki Seisakusho Co., Ltd. or a similar device can be used.
Moreover, the cured product used for the measurement of the elongation recovery rate is produced as follows.
First, a silicone rubber mold with a thickness of 1 mm is placed on a release polyethylene terephthalate (PET) film.
Next, 1 μL of triethanolamine is added to 1 g of the 2-cyanoacrylate-based adhesive composition of the present disclosure, stirred, and poured into the mold.
After pouring the 2-cyanoacrylate adhesive composition, the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and then at a temperature of 25 ° C. and a relative humidity of 50%. Allow 24 hours to fully cure.
After curing, the mold and release PET film are removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
＜本開示の２－シアノアクリレート系接着剤組成物の硬化物の伸長回復率の上昇率＞
上記計算式（１）から求められる本開示の２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬＡ、
伸長回復率ＬＡを測定した上記２－シアノアクリレート系接着剤組成物から多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬａとしたとき、下記式（Ａ）を満たすことが好ましい。
（ＬＡ－Ｌａ／Ｌａ）×１００≧５０％ （Ａ） <Rate of increase in elongation recovery rate of the cured product of the 2-cyanoacrylate adhesive composition of the present disclosure>
The elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (1) is LA,
When La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured, the following formula (A) is preferably satisfied.
(LA−La/La)×100≧50% (A)
上記計算式（１）から求められる本開示の２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬＡ、
伸長回復率ＬＡを測定した上記２－シアノアクリレート系接着剤組成物から多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬａとしたとき、下記式（Ａ）を満たすことが好ましい。
（ＬＡ－Ｌａ／Ｌａ）×１００≧５０％ （Ａ） <Rate of increase in elongation recovery rate of the cured product of the 2-cyanoacrylate adhesive composition of the present disclosure>
The elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (1) is LA,
When La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured, the following formula (A) is preferably satisfied.
(LA−La/La)×100≧50% (A)
上記計算式（２）から求められる本開示の２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬＢ、
伸長回復率ＬＢを測定した上記２－シアノアクリレート系接着剤組成物から多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬｂとしたとき、下記式（Ｂ）を満たすことが好ましい。
（ＬＢ－Ｌｂ／Ｌｂ）×１００≧５０％ （Ｂ） LB is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (2),
When the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb, the following formula (B) is preferably satisfied.
(LB-Lb/Lb)×100≧50% (B)
伸長回復率ＬＢを測定した上記２－シアノアクリレート系接着剤組成物から多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬｂとしたとき、下記式（Ｂ）を満たすことが好ましい。
（ＬＢ－Ｌｂ／Ｌｂ）×１００≧５０％ （Ｂ） LB is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition of the present disclosure obtained from the above formula (2),
When the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb, the following formula (B) is preferably satisfied.
(LB-Lb/Lb)×100≧50% (B)
＜本開示の２－シアノアクリレート系接着剤組成物の用途＞
本開示の２－シアノアクリレート系接着剤組成物は、建築用途、自動車関連用途、電気・電子材料用途等の様々な用途に使用可能である。
建築用途としては、建築用弾性接着剤、複層ガラス用接着剤、人工大理石用接着剤等が挙げられる。また、電気・電子材料用途としては、半導体封止用樹脂、プリント配線基板用絶縁材料、電線・ケーブル用絶縁被覆材、電子部品コーティング剤、電子部品用ポッティング剤、電装シーラー等が挙げられる。また、パッキン、Ｏリング等にも本開示の２－シアノアクリレート系接着剤組成物を使用できる。具体的には、防水パッキン類、防虫パッキン類、クリーナ用の防振・吸音と空気シール材、電気温水器用の防滴カバー、防水パッキン、ヒータ部パッキン、電極部パッキン、安全弁ダイアフラム、電磁弁、スチームオーブンレンジ及びジャー炊飯器用の防水パッキン、給水タンクパッキン、吸水バルブ、水受けパッキン、保温ヒータ部パッキン、蒸気吹き出し口シール等燃焼機器用のオイルパッキン、Ｏリング、ドレインパッキン、送・吸気パッキン、防振ゴム、給油口パッキン、油量計パッキン、ダイアフラム弁等、音響機器用のスピーカーガスケット、スピーカーエッジなどが挙げられる。
また、自動車関連用途としては、ボディ部品として、気密保持のための接着シール材、ガラスの振動防止材、車体部位の防振材、特にウインドシールガスケット、ドアガラス用ガスケット等に使用することができる。エンジン部品としては、エンジンオイル用接着シール材等に使用することができる。さらに、本発明の接着剤組成物は、電気・電子部品、自動車部品の組み付けライン上で液状シール材をロボット等により自動塗布しながら接着シールするガスケット方法［ＭＩＰＧ（Ｍｏｌｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）、ＦＩＰＧ（Ｆｏｒｍｅｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）、ＣＩＰＧ（Ｃｕｒｅｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）］にも使用することができる。 <Application of 2-cyanoacrylate adhesive composition of the present disclosure>
The 2-cyanoacrylate adhesive composition of the present disclosure can be used in various applications such as construction applications, automobile-related applications, and electrical/electronic material applications.
Architectural applications include elastic adhesives for construction, adhesives for double glazing, adhesives for artificial marble, and the like. Examples of electrical/electronic material applications include resins for encapsulating semiconductors, insulating materials for printed wiring boards, insulating coating materials for electric wires and cables, electronic component coating agents, electronic component potting agents, electrical component sealers, and the like. The 2-cyanoacrylate adhesive composition of the present disclosure can also be used for packings, O-rings and the like. Specifically, waterproof packings, insect-proof packings, anti-vibration/sound absorption and air seal materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater packings, electrode packings, safety valve diaphragms, solenoid valves, Waterproof packing for steam oven ranges and jar rice cookers, water tank packing, water absorption valves, water receiving packing, heat insulation heater packing, oil packing for combustion equipment such as steam outlet seals, O-rings, drain packing, feed/intake packing, Anti-vibration rubber, oil fill port packing, oil gauge packing, diaphragm valve, etc., speaker gasket for audio equipment, speaker edge, etc.
In addition, as automobile-related applications, it can be used as an adhesive sealing material for maintaining airtightness as a body part, an anti-vibration material for glass, an anti-vibration material for car body parts, especially a wind seal gasket, a door glass gasket, etc. . As an engine part, it can be used as an adhesive sealing material for engine oil or the like. Furthermore, the adhesive composition of the present invention can be used in a gasket method [MIPG (Mold In Place Gasket), FIPG (Mold In Place Gasket), FIPG ( Formed In Place Gasket), CIPG (Cured In Place Gasket)].
本開示の２－シアノアクリレート系接着剤組成物は、建築用途、自動車関連用途、電気・電子材料用途等の様々な用途に使用可能である。
建築用途としては、建築用弾性接着剤、複層ガラス用接着剤、人工大理石用接着剤等が挙げられる。また、電気・電子材料用途としては、半導体封止用樹脂、プリント配線基板用絶縁材料、電線・ケーブル用絶縁被覆材、電子部品コーティング剤、電子部品用ポッティング剤、電装シーラー等が挙げられる。また、パッキン、Ｏリング等にも本開示の２－シアノアクリレート系接着剤組成物を使用できる。具体的には、防水パッキン類、防虫パッキン類、クリーナ用の防振・吸音と空気シール材、電気温水器用の防滴カバー、防水パッキン、ヒータ部パッキン、電極部パッキン、安全弁ダイアフラム、電磁弁、スチームオーブンレンジ及びジャー炊飯器用の防水パッキン、給水タンクパッキン、吸水バルブ、水受けパッキン、保温ヒータ部パッキン、蒸気吹き出し口シール等燃焼機器用のオイルパッキン、Ｏリング、ドレインパッキン、送・吸気パッキン、防振ゴム、給油口パッキン、油量計パッキン、ダイアフラム弁等、音響機器用のスピーカーガスケット、スピーカーエッジなどが挙げられる。
また、自動車関連用途としては、ボディ部品として、気密保持のための接着シール材、ガラスの振動防止材、車体部位の防振材、特にウインドシールガスケット、ドアガラス用ガスケット等に使用することができる。エンジン部品としては、エンジンオイル用接着シール材等に使用することができる。さらに、本発明の接着剤組成物は、電気・電子部品、自動車部品の組み付けライン上で液状シール材をロボット等により自動塗布しながら接着シールするガスケット方法［ＭＩＰＧ（Ｍｏｌｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）、ＦＩＰＧ（Ｆｏｒｍｅｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）、ＣＩＰＧ（Ｃｕｒｅｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）］にも使用することができる。 <Application of 2-cyanoacrylate adhesive composition of the present disclosure>
The 2-cyanoacrylate adhesive composition of the present disclosure can be used in various applications such as construction applications, automobile-related applications, and electrical/electronic material applications.
Architectural applications include elastic adhesives for construction, adhesives for double glazing, adhesives for artificial marble, and the like. Examples of electrical/electronic material applications include resins for encapsulating semiconductors, insulating materials for printed wiring boards, insulating coating materials for electric wires and cables, electronic component coating agents, electronic component potting agents, electrical component sealers, and the like. The 2-cyanoacrylate adhesive composition of the present disclosure can also be used for packings, O-rings and the like. Specifically, waterproof packings, insect-proof packings, anti-vibration/sound absorption and air seal materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater packings, electrode packings, safety valve diaphragms, solenoid valves, Waterproof packing for steam oven ranges and jar rice cookers, water tank packing, water absorption valves, water receiving packing, heat insulation heater packing, oil packing for combustion equipment such as steam outlet seals, O-rings, drain packing, feed/intake packing, Anti-vibration rubber, oil fill port packing, oil gauge packing, diaphragm valve, etc., speaker gasket for audio equipment, speaker edge, etc.
In addition, as automobile-related applications, it can be used as an adhesive sealing material for maintaining airtightness as a body part, an anti-vibration material for glass, an anti-vibration material for car body parts, especially a wind seal gasket, a door glass gasket, etc. . As an engine part, it can be used as an adhesive sealing material for engine oil or the like. Furthermore, the adhesive composition of the present invention can be used in a gasket method [MIPG (Mold In Place Gasket), FIPG (Mold In Place Gasket), FIPG ( Formed In Place Gasket), CIPG (Cured In Place Gasket)].
また、本開示の２－シアノアクリレート系接着剤組成物は、被接着物として、樹脂又は金属に対し好適に使用することができ、ゴムに対してより好適に使用することができる。
In addition, the 2-cyanoacrylate-based adhesive composition of the present disclosure can be suitably used for resins or metals as adherends, and can be more suitably used for rubber.
以下、上記実施形態を実施例により具体的に説明するが、上記実施形態はこれらの実施例に限定されるものではない。また、以下において「部」は、特に断らない限り、「質量部」を意味する。
Although the above embodiment will be specifically described below with reference to examples, the above embodiment is not limited to these examples. In addition, hereinafter, "parts" means "parts by mass" unless otherwise specified.
各種物性値は、以下のように測定した。
Various physical property values were measured as follows.
＜２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率＞
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置（アントンパール社製、製品名「ＭＣＲ３０１」）を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定した。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とした。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分、相対湿度５０％の条件で、－５０℃～１５０℃の範囲において、ずりによる硬化物の貯蔵弾性率を測定し、硬化物の２５℃における貯蔵弾性率を求めた。
各実施例及び各比較例において使用した２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率（表中においては、２－シアノアクリレート化合物の貯蔵弾性率と記載）を表１にまとめた。 <Storage modulus at 25° C. of cured product obtained by homopolymerizing 2-cyanoacrylate compound>
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301"), frequency 1 Hz, The storage modulus was measured under conditions of a temperature of 25° C. and a thickness of 300 μm.
After confirming that there was no change in the storage modulus of the 2-cyanoacrylate compound, this was used as a cured product of the 2-cyanoacrylate compound. Using the above cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz, a temperature increase rate of 2 ° C./min, and a relative humidity of 50%. The storage elastic modulus at 25°C was determined.
The storage elastic modulus at 25° C. of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example (indicated as the storage elastic modulus of the 2-cyanoacrylate compound in the table) is shown. summarized in 1.
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置（アントンパール社製、製品名「ＭＣＲ３０１」）を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定した。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とした。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分、相対湿度５０％の条件で、－５０℃～１５０℃の範囲において、ずりによる硬化物の貯蔵弾性率を測定し、硬化物の２５℃における貯蔵弾性率を求めた。
各実施例及び各比較例において使用した２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率（表中においては、２－シアノアクリレート化合物の貯蔵弾性率と記載）を表１にまとめた。 <Storage modulus at 25° C. of cured product obtained by homopolymerizing 2-cyanoacrylate compound>
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301"), frequency 1 Hz, The storage modulus was measured under conditions of a temperature of 25° C. and a thickness of 300 μm.
After confirming that there was no change in the storage modulus of the 2-cyanoacrylate compound, this was used as a cured product of the 2-cyanoacrylate compound. Using the above cured product, the storage elastic modulus of the cured product due to shear is measured in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz, a temperature increase rate of 2 ° C./min, and a relative humidity of 50%. The storage elastic modulus at 25°C was determined.
The storage elastic modulus at 25° C. of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example (indicated as the storage elastic modulus of the 2-cyanoacrylate compound in the table) is shown. summarized in 1.
＜２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度＞
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置（アントンパール社製、製品名「ＭＣＲ３０１」）を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定した。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とした。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分の条件で、－５０℃～１５０℃の範囲において、動的粘弾性スペクトルを求め、損失正接（ｔａｎδ）が最大値となる温度を測定した。ピークが２つ以上観察される場合、最も大きいピークとなる損失正接（ｔａｎδ）を極大値とした。
各実施例及び各比較例において使用した２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度（表中においては、２－シアノアクリレート化合物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度（℃）と記載）を表１にまとめた。 <Temperature showing maximum loss tangent (tan δ (max)) of cured product obtained by homopolymerizing 2-cyanoacrylate compound>
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301"), frequency 1 Hz, The storage modulus was measured under conditions of a temperature of 25° C. and a thickness of 300 μm.
After confirming that there was no change in the storage modulus of the 2-cyanoacrylate compound, this was used as a cured product of the 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz and a temperature increase rate of 2 ° C./min, and determine the temperature at which the loss tangent (tan δ) becomes the maximum value. It was measured. When two or more peaks were observed, the loss tangent (tan δ) that was the largest peak was taken as the maximum value.
The temperature at which the loss tangent maximum value (tan δ (max)) of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example is shown (in the table, the temperature of the 2-cyanoacrylate compound Table 1 summarizes the temperature (° C.) indicating the maximum value of the loss tangent (tan δ (max)).
２－シアノアクリレート化合物を、トリエタノールアミンを塗布した動的粘弾性測定装置冶具間に注入後、動的粘弾性測定装置（アントンパール社製、製品名「ＭＣＲ３０１」）を用いて、周波数１Ｈｚ、温度２５℃、厚み３００μｍの条件下、貯蔵弾性率を測定した。
２－シアノアクリレート化合物の貯蔵弾性率の変化がなくなったことを確認し、これを２－シアノアクリレート化合物の硬化物とした。上記硬化物を用い、周波数１Ｈｚ、昇温速度２℃／分の条件で、－５０℃～１５０℃の範囲において、動的粘弾性スペクトルを求め、損失正接（ｔａｎδ）が最大値となる温度を測定した。ピークが２つ以上観察される場合、最も大きいピークとなる損失正接（ｔａｎδ）を極大値とした。
各実施例及び各比較例において使用した２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度（表中においては、２－シアノアクリレート化合物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度（℃）と記載）を表１にまとめた。 <Temperature showing maximum loss tangent (tan δ (max)) of cured product obtained by homopolymerizing 2-cyanoacrylate compound>
After injecting the 2-cyanoacrylate compound between the dynamic viscoelasticity measuring device jigs coated with triethanolamine, using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301"), frequency 1 Hz, The storage modulus was measured under conditions of a temperature of 25° C. and a thickness of 300 μm.
After confirming that there was no change in the storage modulus of the 2-cyanoacrylate compound, this was used as a cured product of the 2-cyanoacrylate compound. Using the above cured product, obtain a dynamic viscoelastic spectrum in the range of -50 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz and a temperature increase rate of 2 ° C./min, and determine the temperature at which the loss tangent (tan δ) becomes the maximum value. It was measured. When two or more peaks were observed, the loss tangent (tan δ) that was the largest peak was taken as the maximum value.
The temperature at which the loss tangent maximum value (tan δ (max)) of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example is shown (in the table, the temperature of the 2-cyanoacrylate compound Table 1 summarizes the temperature (° C.) indicating the maximum value of the loss tangent (tan δ (max)).
（実施例１～実施例８）
表１に記載の２－シアノアクリレート化合物１００部に、表１に記載の多官能シアノアクリレート化合物を表１に記載の含有量となるように配合し、均一になるまで攪拌し、２－シアノアクリレート系接着剤組成物を製造した。 (Examples 1 to 8)
To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
表１に記載の２－シアノアクリレート化合物１００部に、表１に記載の多官能シアノアクリレート化合物を表１に記載の含有量となるように配合し、均一になるまで攪拌し、２－シアノアクリレート系接着剤組成物を製造した。 (Examples 1 to 8)
To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
（比較例１～比較例４及び比較例８）
表１に記載の２－シアノアクリレート化合物を接着剤組成物とした。 (Comparative Examples 1 to 4 and Comparative Example 8)
A 2-cyanoacrylate compound shown in Table 1 was used as an adhesive composition.
表１に記載の２－シアノアクリレート化合物を接着剤組成物とした。 (Comparative Examples 1 to 4 and Comparative Example 8)
A 2-cyanoacrylate compound shown in Table 1 was used as an adhesive composition.
（比較例５～比較例７及び比較例９）
表１に記載の２－シアノアクリレート化合物１００部に、表１に記載の多官能シアノアクリレート化合物を表１に記載の含有量となるように配合し、均一になるまで攪拌し、２－シアノアクリレート系接着剤組成物を製造した。 (Comparative Examples 5 to 7 and 9)
To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
表１に記載の２－シアノアクリレート化合物１００部に、表１に記載の多官能シアノアクリレート化合物を表１に記載の含有量となるように配合し、均一になるまで攪拌し、２－シアノアクリレート系接着剤組成物を製造した。 (Comparative Examples 5 to 7 and 9)
To 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 is blended so as to have the content described in Table 1, stirred until uniform, and the 2-cyanoacrylate A system adhesive composition was prepared.
表１中における多官能シアノアクリレートの略号の詳細は、以下の通りである。
・ＰＰＧ４０００ＴＣＡ：３官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ４，０００）－トリスシアノアクリレート）、Ｍｎ４，６４０
・ＰＰＧ３０００ＢＣＡ：２官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ３，０００）－ビスシアノアクリレート）、Ｍｎ４，０３５
・ＰＰＧ１００００ＢＣＡ：２官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ１０，０００）－ビスシアノアクリレート）、Ｍｎ１９，７００ Details of the abbreviations of polyfunctional cyanoacrylates in Table 1 are as follows.
・PPG4000TCA: trifunctional 2-cyanoacrylate compound (PPG (Mn4,000)-tris cyanoacrylate), Mn4,640
・PPG3000BCA: Bifunctional 2-cyanoacrylate compound (PPG (Mn3,000)-biscyanoacrylate), Mn4,035
・PPG10000BCA: Bifunctional 2-cyanoacrylate compound (PPG (Mn10,000)-biscyanoacrylate), Mn19,700
・ＰＰＧ４０００ＴＣＡ：３官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ４，０００）－トリスシアノアクリレート）、Ｍｎ４，６４０
・ＰＰＧ３０００ＢＣＡ：２官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ３，０００）－ビスシアノアクリレート）、Ｍｎ４，０３５
・ＰＰＧ１００００ＢＣＡ：２官能２－シアノアクリレート化合物（ＰＰＧ（Ｍｎ１０，０００）－ビスシアノアクリレート）、Ｍｎ１９，７００ Details of the abbreviations of polyfunctional cyanoacrylates in Table 1 are as follows.
・PPG4000TCA: trifunctional 2-cyanoacrylate compound (PPG (Mn4,000)-tris cyanoacrylate), Mn4,640
・PPG3000BCA: Bifunctional 2-cyanoacrylate compound (PPG (Mn3,000)-biscyanoacrylate), Mn4,035
・PPG10000BCA: Bifunctional 2-cyanoacrylate compound (PPG (Mn10,000)-biscyanoacrylate), Mn19,700
なお、ＰＰＧ４０００ＴＣＡは、下記方法により合成した。
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；４０００（カタログ値）、ポリエーテルトリオール型、ＡＤＥＫＡ社製、商品名「アデカポリエーテルＧ－４０００」］２５．２ｇを１６ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ４０００ＴＣＡ）２８．１ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG4000TCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. After that, the reaction system was heated to 60° C., and while blowing nitrogen gas from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; Polyether G-4000"] dissolved in 16 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 28.1 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG4000TCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；４０００（カタログ値）、ポリエーテルトリオール型、ＡＤＥＫＡ社製、商品名「アデカポリエーテルＧ－４０００」］２５．２ｇを１６ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ４０００ＴＣＡ）２８．１ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG4000TCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. After that, the reaction system was heated to 60° C., and while blowing nitrogen gas from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; Polyether G-4000"] dissolved in 16 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 28.1 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG4000TCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
なお、ＰＰＧ３０００ＢＣＡは、下記方法により合成した。
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；３０００（カタログ値）、両末端ヒドロキシ基型、ＡＤＥＫＡ社製、商品名「アデカポリオールＰ－３０００」］２８．４ｇを１８ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ３０００ＢＣＡ）３１．１ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG3000BCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the reaction system was heated to 60° C., and while blowing nitrogen gas through a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; ADEKA POLYOL P-3000"] dissolved in 18 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 31.1 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG3000BCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；３０００（カタログ値）、両末端ヒドロキシ基型、ＡＤＥＫＡ社製、商品名「アデカポリオールＰ－３０００」］２８．４ｇを１８ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ３０００ＢＣＡ）３１．１ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG3000BCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the reaction system was heated to 60° C., and while blowing nitrogen gas through a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; ADEKA POLYOL P-3000"] dissolved in 18 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 31.1 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG3000BCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
なお、ＰＰＧ１００００ＢＣＡは、下記方法により合成した。
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；１００００（カタログ値）、両末端ヒドロキシ基型、ＡＧＣ社製、商品名「プレミノールＳ－４０１１」］９４．５ｇを６０ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ１００００ＢＣＡ）９７．８ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG10000BCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the temperature of the reaction system is raised to 60° C., and while nitrogen gas is blown from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; A solution of 94.5 g of Preminol S-4011"] dissolved in 60 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 97.8 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG10000BCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
攪拌機、温度計、リービッヒ冷却管、窒素吹き込み管及び滴下ロートを備える容量５００ｍＬのフラスコに、シアノアクリル酸クロライド２．４０ｇ（２０．８ミリモル）と、ベンゼン１３５ｍＬとを仕込んだ。その後、反応系を６０℃に昇温させ、窒素吹き込み管から窒素ガスを吹き込みながら、ポリオキシプロピレングリコール［数平均分子量；１００００（カタログ値）、両末端ヒドロキシ基型、ＡＧＣ社製、商品名「プレミノールＳ－４０１１」］９４．５ｇを６０ｍＬのベンゼンに溶解させた溶液を加えた。
次いで、温度を６０℃に維持し、３０分間攪拌した。その後、２５℃まで冷却後、減圧下、ベンゼンを留去して、無色で粘ちょうなオイル状の多官能シアノアクリレート（ＰＰＧ１００００ＢＣＡ）９７．８ｇを得た。なお、ベンゼンとしては乾燥ベンゼンを使用し、ガラス器具は十分加熱乾燥させたものを用いた。 PPG10000BCA was synthesized by the following method.
A 500 mL flask equipped with a stirrer, thermometer, Liebig condenser, nitrogen blowing tube and dropping funnel was charged with 2.40 g (20.8 mmol) of cyanoacryloyl chloride and 135 mL of benzene. Thereafter, the temperature of the reaction system is raised to 60° C., and while nitrogen gas is blown from a nitrogen blowing pipe, polyoxypropylene glycol [number average molecular weight; A solution of 94.5 g of Preminol S-4011"] dissolved in 60 mL of benzene was added.
The temperature was then maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25° C., benzene was distilled off under reduced pressure to obtain 97.8 g of a colorless, viscous, oily polyfunctional cyanoacrylate (PPG10000BCA). Dried benzene was used as benzene, and the glassware used was sufficiently heated and dried.
＜伸長回復率の評価＞
離型ポリエチレンテレフタレート（ＰＥＴ）フィルム（帝人フィルムソリューション株式会社製、製品名「ピューレックス（登録商標）Ａ３１」）上に、厚さ１ｍｍのシリコーンゴムの型枠を配置した。
上記実施例及び比較例において製造した接着剤組成物１ｇに、トリエタノールアミンを１μＬ添加し、撹拌した後、上記型枠内へ流し込んだ。
接着剤組成物の流し込み後、型枠及び接着剤組成物上に、別途用意した上記離型ＰＥＴフィルムを被せ、ガラス板で挟み込んだ後、温度２５℃、相対湿度５０％で２４時間静置し、完全に硬化させた。
硬化後、型枠及び離型ＰＥＴフィルムを取り除いて、幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を得た。 <Evaluation of elongation recovery rate>
A silicone rubber mold with a thickness of 1 mm was placed on a release polyethylene terephthalate (PET) film (manufactured by Teijin Film Solution Co., Ltd., product name “Purex (registered trademark) A31”).
1 μL of triethanolamine was added to 1 g of the adhesive compositions produced in the above Examples and Comparative Examples, and after stirring, the mixture was poured into the mold.
After pouring the adhesive composition, the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and allowed to stand at a temperature of 25 ° C. and a relative humidity of 50% for 24 hours. , fully cured.
After curing, the mold and release PET film were removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
離型ポリエチレンテレフタレート（ＰＥＴ）フィルム（帝人フィルムソリューション株式会社製、製品名「ピューレックス（登録商標）Ａ３１」）上に、厚さ１ｍｍのシリコーンゴムの型枠を配置した。
上記実施例及び比較例において製造した接着剤組成物１ｇに、トリエタノールアミンを１μＬ添加し、撹拌した後、上記型枠内へ流し込んだ。
接着剤組成物の流し込み後、型枠及び接着剤組成物上に、別途用意した上記離型ＰＥＴフィルムを被せ、ガラス板で挟み込んだ後、温度２５℃、相対湿度５０％で２４時間静置し、完全に硬化させた。
硬化後、型枠及び離型ＰＥＴフィルムを取り除いて、幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を得た。 <Evaluation of elongation recovery rate>
A silicone rubber mold with a thickness of 1 mm was placed on a release polyethylene terephthalate (PET) film (manufactured by Teijin Film Solution Co., Ltd., product name “Purex (registered trademark) A31”).
1 μL of triethanolamine was added to 1 g of the adhesive compositions produced in the above Examples and Comparative Examples, and after stirring, the mixture was poured into the mold.
After pouring the adhesive composition, the mold and the adhesive composition were covered with the separately prepared release PET film, sandwiched between glass plates, and allowed to stand at a temperature of 25 ° C. and a relative humidity of 50% for 24 hours. , fully cured.
After curing, the mold and release PET film were removed to obtain a cured product with a width of 5 mm, a length of 50 mm and a thickness of 1 mm.
引張試験機（株式会社東洋精機製作所製、製品名「ストログラフＶ２０－Ｃ」）を用い、治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付けた硬化物を、治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った。
治具の固定を解除した後、１分、５分、３０分経過したときのそれぞれの印間の長さ（Ｌ２）を測定し、下記計算式から伸長回復率（％）を算出した。算出結果を表１に示す。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ Using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Strograph V20-C"), the cured product was fixed at a distance between jigs of 20 mm (L 0 ), and the jig fixing position was marked. It was pulled at a tensile speed of 20 mm/min until the distance between jigs reached 40 mm (L 1 ).
The length (L 2 ) between marks was measured at 1 minute, 5 minutes, and 30 minutes after releasing the fixation of the jig, and the elongation recovery rate (%) was calculated from the following formula. Table 1 shows the calculation results.
Elongation recovery rate (%): {(L 1 −L 2 )/(L 1 −L 0 )}×100
治具の固定を解除した後、１分、５分、３０分経過したときのそれぞれの印間の長さ（Ｌ２）を測定し、下記計算式から伸長回復率（％）を算出した。算出結果を表１に示す。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ Using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Strograph V20-C"), the cured product was fixed at a distance between jigs of 20 mm (L 0 ), and the jig fixing position was marked. It was pulled at a tensile speed of 20 mm/min until the distance between jigs reached 40 mm (L 1 ).
The length (L 2 ) between marks was measured at 1 minute, 5 minutes, and 30 minutes after releasing the fixation of the jig, and the elongation recovery rate (%) was calculated from the following formula. Table 1 shows the calculation results.
Elongation recovery rate (%): {(L 1 −L 2 )/(L 1 −L 0 )}×100
実施例１において製造した２－シアノアクリレート系接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ１）と、比較例１において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ１）とから、伸長回復率の上昇率（（ＬＡ１－Ｌａ１／Ｌａ１）×１００）を求めたところ、９３％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、９４％、９０％であった。
実施例２において製造した２－シアノアクリレート系接着剤組成物についても、実施例１と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、９０％、９４％、９０％であった。
実施例３において製造した２－シアノアクリレート系接着剤組成物についても、実施例１と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、９０％、９１％、８５％であった。
実施例４において製造した２－シアノアクリレート系接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ２）と、比較例２において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ２）とから、伸長回復率の上昇率（（ＬＡ２－Ｌａ２／Ｌａ２）×１００）を求めたところ、１０７％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、１３８％、１０６％であった。
実施例５において製造した２－シアノアクリレート系接着剤組成物についても、実施例４と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、１１４％、１４８％、１１１％であった。
実施例６において製造した２－シアノアクリレート系接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ３）と、比較例３において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ３）とから、伸長回復率の上昇率（（ＬＡ３－Ｌａ３／Ｌａ３）×１００）を求めたところ、５８％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、７５％、４９％であった。
実施例７において製造した２－シアノアクリレート系接着剤組成物についても、実施例６と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、６０％、７１％、４５％であった。
実施例８において製造した２－シアノアクリレート系接着剤組成物についても、実施例６と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、５０％、６５％、４２％であった。
比較例５において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ５）と、比較例４において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ４）とから、伸長回復率の上昇率（（ＬＡ５－Ｌａ４／Ｌａ４）×１００）を求めたところ、１３％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、２８％、３７％であった。
比較例６において製造した２－シアノアクリレート系接着剤組成物についても、比較例５と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、１５％、２８％、２８％であった。
比較例９において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ９）と、比較例８において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ８）とから、伸長回復率の上昇率（（ＬＡ９－Ｌａ８／Ｌａ８）×１００）を求めたところ、４６％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、４９％、６０％であった。 The elongation recovery rate (LA1) after 1 minute from the release of the fixture of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 1, and the recovery rate (LA1) produced in Comparative Example 1 From the elongation recovery rate (La1) after 1 minute from the fixation of the cured product prepared using the adhesive composition from the jig, the increase rate of the elongation recovery rate ((LA1-La1/La1) × 100 ) was found to be 93%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the increase rate of the elongation recovery rate was obtained in the same manner as described above, it was 94% and 90%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 2, in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 94%, and 90%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 3, in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 91% and 85%, respectively.
The elongation recovery rate (LA2) after 1 minute from the fixing of the jig of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 4 and the recovery rate (LA2) produced in Comparative Example 2 From the elongation recovery rate (La2) one minute after the fixture of the cured product prepared using the adhesive composition was released from the jig, the increase rate of the elongation recovery rate ((LA2-La2/La2) × 100 ) was found to be 107%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 138% and 106%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 5, in the same manner as in Example 4, elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released When the rate of increase of was obtained, they were 114%, 148%, and 111%, respectively.
The elongation recovery rate (LA3) after 1 minute from the release of the fixture of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 6, and the recovery rate (LA3) produced in Comparative Example 3 From the elongation recovery rate (La3) after 1 minute from the fixing of the jig of the cured product prepared using the adhesive composition, the increase rate of the elongation recovery rate ((LA3 - La3 / La3) × 100 ) was found to be 58%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, it was 75% and 49%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 7, in the same manner as in Example 6, elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released When the rate of increase of was obtained, they were 60%, 71%, and 45%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 8, in the same manner as in Example 6, the elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released. When the rate of increase of was obtained, they were 50%, 65%, and 42%, respectively.
The elongation recovery rate (LA5) after 1 minute from the release of the fixture of the cured product produced using the adhesive composition produced in Comparative Example 5 and the adhesive composition produced in Comparative Example 4 Elongation recovery rate increase rate ((LA5-La4/La4) x 100) was obtained from the elongation recovery rate (La4) after 1 minute from the fixation of the jig of the cured product prepared using , 13%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 28% and 37%, respectively.
Regarding the 2-cyanoacrylate adhesive composition produced in Comparative Example 6, in the same manner as in Comparative Example 5, the elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig When the rate of increase of was obtained, they were 15%, 28%, and 28%, respectively.
The elongation recovery rate (LA9) after 1 minute from the release of the fixture of the cured product produced using the adhesive composition produced in Comparative Example 9 and the adhesive composition produced in Comparative Example 8 Elongation recovery rate increase rate ((LA9-La8/La8) x 100) was obtained from the elongation recovery rate (La8) after 1 minute from the fixation of the jig of the cured product prepared using , 46%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 49% and 60%, respectively.
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、９４％、９０％であった。
実施例２において製造した２－シアノアクリレート系接着剤組成物についても、実施例１と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、９０％、９４％、９０％であった。
実施例３において製造した２－シアノアクリレート系接着剤組成物についても、実施例１と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、９０％、９１％、８５％であった。
実施例４において製造した２－シアノアクリレート系接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ２）と、比較例２において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ２）とから、伸長回復率の上昇率（（ＬＡ２－Ｌａ２／Ｌａ２）×１００）を求めたところ、１０７％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、１３８％、１０６％であった。
実施例５において製造した２－シアノアクリレート系接着剤組成物についても、実施例４と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、１１４％、１４８％、１１１％であった。
実施例６において製造した２－シアノアクリレート系接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ３）と、比較例３において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ３）とから、伸長回復率の上昇率（（ＬＡ３－Ｌａ３／Ｌａ３）×１００）を求めたところ、５８％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、７５％、４９％であった。
実施例７において製造した２－シアノアクリレート系接着剤組成物についても、実施例６と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、６０％、７１％、４５％であった。
実施例８において製造した２－シアノアクリレート系接着剤組成物についても、実施例６と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、５０％、６５％、４２％であった。
比較例５において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ５）と、比較例４において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ４）とから、伸長回復率の上昇率（（ＬＡ５－Ｌａ４／Ｌａ４）×１００）を求めたところ、１３％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、２８％、３７％であった。
比較例６において製造した２－シアノアクリレート系接着剤組成物についても、比較例５と同様にして、治具の固定を解除からの経過時間後、１分、５分及び３０分の伸長回復率の上昇率を求めたところ、それぞれ、１５％、２８％、２８％であった。
比較例９において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（ＬＡ９）と、比較例８において製造した接着剤組成物を使用して作製した硬化物の治具の固定を解除から１分経過後の伸長回復率（Ｌａ８）とから、伸長回復率の上昇率（（ＬＡ９－Ｌａ８／Ｌａ８）×１００）を求めたところ、４６％であった。
また、治具の固定を解除からの経過時間を５分、３０分に変更し、上記同様に、伸長回復率の上昇率を求めたところ、それぞれ、４９％、６０％であった。 The elongation recovery rate (LA1) after 1 minute from the release of the fixture of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 1, and the recovery rate (LA1) produced in Comparative Example 1 From the elongation recovery rate (La1) after 1 minute from the fixation of the cured product prepared using the adhesive composition from the jig, the increase rate of the elongation recovery rate ((LA1-La1/La1) × 100 ) was found to be 93%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the increase rate of the elongation recovery rate was obtained in the same manner as described above, it was 94% and 90%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 2, in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 94%, and 90%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 3, in the same manner as in Example 1, elongation recovery rates of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig were 90%, 91% and 85%, respectively.
The elongation recovery rate (LA2) after 1 minute from the fixing of the jig of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 4 and the recovery rate (LA2) produced in Comparative Example 2 From the elongation recovery rate (La2) one minute after the fixture of the cured product prepared using the adhesive composition was released from the jig, the increase rate of the elongation recovery rate ((LA2-La2/La2) × 100 ) was found to be 107%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 138% and 106%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 5, in the same manner as in Example 4, elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released When the rate of increase of was obtained, they were 114%, 148%, and 111%, respectively.
The elongation recovery rate (LA3) after 1 minute from the release of the fixture of the cured product produced using the 2-cyanoacrylate adhesive composition produced in Example 6, and the recovery rate (LA3) produced in Comparative Example 3 From the elongation recovery rate (La3) after 1 minute from the fixing of the jig of the cured product prepared using the adhesive composition, the increase rate of the elongation recovery rate ((LA3 - La3 / La3) × 100 ) was found to be 58%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, it was 75% and 49%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 7, in the same manner as in Example 6, elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released When the rate of increase of was obtained, they were 60%, 71%, and 45%, respectively.
For the 2-cyanoacrylate adhesive composition produced in Example 8, in the same manner as in Example 6, the elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the jig was released. When the rate of increase of was obtained, they were 50%, 65%, and 42%, respectively.
The elongation recovery rate (LA5) after 1 minute from the release of the fixture of the cured product produced using the adhesive composition produced in Comparative Example 5 and the adhesive composition produced in Comparative Example 4 Elongation recovery rate increase rate ((LA5-La4/La4) x 100) was obtained from the elongation recovery rate (La4) after 1 minute from the fixation of the jig of the cured product prepared using , 13%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 28% and 37%, respectively.
Regarding the 2-cyanoacrylate adhesive composition produced in Comparative Example 6, in the same manner as in Comparative Example 5, the elongation recovery rate of 1 minute, 5 minutes, and 30 minutes after the elapsed time from releasing the fixation of the jig When the rate of increase of was obtained, they were 15%, 28%, and 28%, respectively.
The elongation recovery rate (LA9) after 1 minute from the release of the fixture of the cured product produced using the adhesive composition produced in Comparative Example 9 and the adhesive composition produced in Comparative Example 8 Elongation recovery rate increase rate ((LA9-La8/La8) x 100) was obtained from the elongation recovery rate (La8) after 1 minute from the fixation of the jig of the cured product prepared using , 46%.
Further, when the elapsed time from releasing the fixation of the jig was changed to 5 minutes and 30 minutes, and the rate of increase in the elongation recovery rate was obtained in the same manner as above, they were 49% and 60%, respectively.
以上から、実施例において製造した２－シアノアクリレート系接着剤組成物は、硬化物の伸長回復率の上昇率に優れることが分かる。
また、各実施例において製造した２－シアノアクリレート系接着剤組成物は、治具の固定を解除から５分経過の時点で、硬化物の伸長回復が大きく進んでいるため、治具の固定を解除から３０分経過の時点における伸長回復率の上昇率は、５分経過の時点における伸長回復率の上昇率に比べ小さい値となった。
各実施例及び比較例の伸長回復率の上昇率を表１にまとめた。
なお、伸長回復率の上昇率の基準となる比較例１～比較例４及び比較例８についてはいずれも「１」と表１に記載した。
From the above, it can be seen that the 2-cyanoacrylate adhesive compositions produced in Examples are excellent in the rate of increase in elongation recovery rate of the cured product.
In addition, in the 2-cyanoacrylate adhesive composition produced in each example, the recovery of elongation of the cured product has progressed greatly 5 minutes after the fixation of the jig was released. The rate of increase in the elongation recovery rate at 30 minutes after the release was smaller than the rate of increase in elongation recovery rate at the time of 5 minutes.
Table 1 summarizes the rate of increase in the elongation recovery rate of each example and comparative example.
Comparative Examples 1 to 4 and Comparative Example 8, which serve as the reference for the rate of increase in elongation recovery rate, are all listed as "1" in Table 1.
また、各実施例において製造した２－シアノアクリレート系接着剤組成物は、治具の固定を解除から５分経過の時点で、硬化物の伸長回復が大きく進んでいるため、治具の固定を解除から３０分経過の時点における伸長回復率の上昇率は、５分経過の時点における伸長回復率の上昇率に比べ小さい値となった。
各実施例及び比較例の伸長回復率の上昇率を表１にまとめた。
なお、伸長回復率の上昇率の基準となる比較例１～比較例４及び比較例８についてはいずれも「１」と表１に記載した。
From the above, it can be seen that the 2-cyanoacrylate adhesive compositions produced in Examples are excellent in the rate of increase in elongation recovery rate of the cured product.
In addition, in the 2-cyanoacrylate adhesive composition produced in each example, the recovery of elongation of the cured product has progressed greatly 5 minutes after the fixation of the jig was released. The rate of increase in the elongation recovery rate at 30 minutes after the release was smaller than the rate of increase in elongation recovery rate at the time of 5 minutes.
Table 1 summarizes the rate of increase in the elongation recovery rate of each example and comparative example.
Comparative Examples 1 to 4 and Comparative Example 8, which serve as the reference for the rate of increase in elongation recovery rate, are all listed as "1" in Table 1.
表１から、実施例において製造した２－シアノアクリレート系接着剤組成物は、比較例において製造した接着剤組成物に比べて、硬化物の伸長回復率及びその上昇率が優れていることが分かる。
From Table 1, it can be seen that the 2-cyanoacrylate adhesive compositions produced in Examples are superior to the adhesive compositions produced in Comparative Examples in the elongation recovery rate of the cured product and its increase rate. .
２０２１年７月１２日に出願された日本国特許出願２０２１－１１５３４７号の開示は、その全体が参照により本明細書に取り込まれる。本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記載された場合と同程度に、本明細書に参照により取り込まれる。
The disclosure of Japanese Patent Application No. 2021-115347 filed on July 12, 2021 is incorporated herein by reference in its entirety. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.
Claims (13)
- ２－シアノアクリレート化合物と、多官能シアノアクリレート化合物とを含有し、
前記２－シアノアクリレート化合物を単独重合してなる硬化物の２５℃における貯蔵弾性率が１．０×１０７Ｐａより大きく５．０×１０７Ｐａ以下であり、
前記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオール、アクリルポリオール、ポリウレタンポリオール、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、フェノール樹脂、両末端にヒドロキシ基を有するシラン化合物及び両末端にヒドロキシ基を有するシロキサン化合物からなる群より選択される化合物の２－シアノアクリル酸エステルを少なくとも１種含む、２－シアノアクリレート系接着剤組成物。 containing a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound,
A cured product obtained by homopolymerizing the 2-cyanoacrylate compound has a storage modulus at 25° C. of greater than 1.0×10 7 Pa and not more than 5.0×10 7 Pa,
The polyfunctional cyanoacrylate compound is polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, acrylic polyol, polyurethane polyol, polyvinyl formal, polyvinyl butyral, polyvinyl A 2-cyanoacrylate system containing at least one 2-cyanoacrylic acid ester of a compound selected from the group consisting of alcohols, phenolic resins, silane compounds having hydroxyl groups at both ends, and siloxane compounds having hydroxyl groups at both ends. adhesive composition. - 前記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、前記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、前記治具の固定を解除し、１分経過したときの前記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）が５５％以上である、請求項１に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a jig distance of 20 mm (L0), and the jig fixed position is marked, and after pulling at a tensile speed of 20 mm / min until the distance between the jigs becomes 40 mm (L1), the fixation of the jig is released, and the length between the marks when 1 minute has passed 2. The 2-cyanoacrylate adhesive composition according to claim 1, wherein the elongation recovery rate (%) obtained from the following formula (1) is 55% or more by measuring the thickness (L2).
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1) - 前記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、前記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、前記治具の固定を解除し、１分経過したときの前記印間の長さ（Ｌ２）を測定し、下記計算式（１）から求められる伸長回復率（％）をＬＡ、
伸長回復率ＬＡを測定した前記２－シアノアクリレート系接着剤組成物から前記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬａとしたとき、下記式（Ａ）を満たす、請求項２に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ２）／（Ｌ１－Ｌ０）｝×１００ （１）
（ＬＡ－Ｌａ／Ｌａ）×１００≧５０％ （Ａ） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a jig distance of 20 mm (L0), and the jig fixed position is marked, and after pulling at a tensile speed of 20 mm / min until the distance between the jigs becomes 40 mm (L1), the fixation of the jig is released, and the length between the marks when 1 minute has passed The length (L2) is measured, and the elongation recovery rate (%) obtained from the following formula (1) is LA,
When La is the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LA was measured, the following is obtained. 3. The 2-cyanoacrylate adhesive composition according to claim 2, which satisfies formula (A).
Elongation recovery rate (%): {(L1-L2) / (L1-L0)} × 100 (1)
(LA−La/La)×100≧50% (A) - 前記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、前記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、前記治具の固定を解除し、５分経過したときの前記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）が６５％以上である、請求項１～請求項３のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a jig distance of 20 mm (L0), and the jig fixed position , and after pulling at a tensile speed of 20 mm / min until the distance between the jigs becomes 40 mm (L1), the jig is released, and the length between the marks when 5 minutes have passed The 2-cyanoacrylate system according to any one of claims 1 to 3, wherein the elongation recovery rate (%) obtained from the following formula (2) is 65% or more by measuring the length (L3). adhesive composition.
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2) - 前記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、治具固定位置に印を付け、前記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、前記治具の固定を解除し、５分経過したときの前記印間の長さ（Ｌ３）を測定し、下記計算式（２）から求められる伸長回復率（％）をＬＢ、
伸長回復率ＬＢを測定した前記２－シアノアクリレート系接着剤組成物から前記多官能シアノアクリレート化合物を除いた２－シアノアクリレート系接着剤組成物の伸長回復率（％）をＬｂとしたとき、下記式（Ｂ）を満たす、請求項４に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ３）／（Ｌ１－Ｌ０）｝×１００ （２）
（ＬＢ－Ｌｂ／Ｌｂ）×１００≧５０％ （Ｂ） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition was fixed to a tensile tester with a jig distance of 20 mm (L0), and the jig fixed position , and after pulling at a tensile speed of 20 mm / min until the distance between the jigs becomes 40 mm (L1), the jig is released, and the length between the marks when 5 minutes have passed The length (L3) is measured, and the elongation recovery rate (%) obtained from the following formula (2) is LB,
When the elongation recovery rate (%) of the 2-cyanoacrylate adhesive composition excluding the polyfunctional cyanoacrylate compound from the 2-cyanoacrylate adhesive composition for which the elongation recovery rate LB was measured is Lb, the following is obtained. 5. The 2-cyanoacrylate adhesive composition according to claim 4, which satisfies formula (B).
Elongation recovery rate (%): {(L1-L3) / (L1-L0)} × 100 (2)
(LB-Lb/Lb)×100≧50% (B) - 前記２－シアノアクリレート系接着剤組成物を硬化してなる幅５ｍｍ、長さ５０ｍｍ、厚さ１ｍｍの硬化物を、引張試験機に治具間距離２０ｍｍ（Ｌ０）として固定し、印を付け、前記治具間距離が４０ｍｍ（Ｌ１）となるまで、２０ｍｍ／分の引張速度で引っ張った後、前記治具の固定を解除し、３０分経過したときの前記印間の長さ（Ｌ４）を測定し、下記計算式（３）から求められる伸長回復率（％）が７０％以上である、請求項１～請求項５のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。
伸長回復率（％）：｛（Ｌ１－Ｌ４）／（Ｌ１－Ｌ０）｝×１００ （３） A cured product having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm obtained by curing the 2-cyanoacrylate adhesive composition is fixed to a tensile tester with a distance between jigs of 20 mm (L0) and marked, After pulling at a tensile speed of 20 mm/min until the distance between the jigs reaches 40 mm (L1), the jig is released, and the length (L4) between the marks is measured after 30 minutes. 6. The 2-cyanoacrylate adhesive composition according to any one of claims 1 to 5, which has an elongation recovery rate (%) of 70% or more measured and calculated from the following formula (3).
Elongation recovery rate (%): {(L1-L4) / (L1-L0)} × 100 (3) - 前記２－シアノアクリレート化合物１００質量部に対し、前記多官能シアノアクリレート化合物を２質量部～５０質量部含有する、請求項１～請求項６のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。 The 2-cyanoacrylate adhesive according to any one of claims 1 to 6, which contains 2 parts by mass to 50 parts by mass of the polyfunctional cyanoacrylate compound with respect to 100 parts by mass of the 2-cyanoacrylate compound. agent composition.
- 前記２－シアノアクリレート化合物が、エーテル結合を有する、請求項１～請求項７のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。 The 2-cyanoacrylate adhesive composition according to any one of claims 1 to 7, wherein the 2-cyanoacrylate compound has an ether bond.
- 前記２－シアノアクリレート化合物が、前記エーテル結合を２つ以上有する、請求項８に記載の２－シアノアクリレート系接着剤組成物。 The 2-cyanoacrylate adhesive composition according to claim 8, wherein the 2-cyanoacrylate compound has two or more of the ether bonds.
- 前記２－シアノアクリレート化合物が、下記式（１）で表される化合物を含む、請求項１～請求項９のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。
式（１）中、
Ｌ１はそれぞれ独立に、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（Ｒ１）ＣＨ２－又は－ＣＨ２ＣＨ（Ｒ１）－を表し、
Ｒ１は置換基を有してもよい炭素数１～６の直鎖又は分岐のアルキル基を表し、
Ｒ２は置換基を有してもよい炭素数１～１５の直鎖又は分岐のアルキル基を表し、
ｐは１～５の整数を表す。 The 2-cyanoacrylate adhesive composition according to any one of claims 1 to 9, wherein the 2-cyanoacrylate compound contains a compound represented by the following formula (1).
In formula (1),
L 1 each independently represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(R 1 )CH 2 - or -CH 2 CH(R 1 )-;
R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent;
R 2 represents a linear or branched alkyl group having 1 to 15 carbon atoms which may have a substituent;
p represents an integer of 1 to 5; - 前記２－シアノアクリレート化合物を単独重合してなる硬化物の損失正接の極大値（ｔａｎδ（ｍａｘ））を示す温度が、８０℃以下である、請求項１～請求項１０のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。 The temperature at which the loss tangent maximum value (tan δ (max)) of the cured product obtained by homopolymerizing the 2-cyanoacrylate compound is 80° C. or less, according to any one of claims 1 to 10. The 2-cyanoacrylate adhesive composition described.
- 前記多官能シアノアクリレート化合物の数平均分子量が１，０００～５０，０００である、請求項１～請求項１１のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。 The 2-cyanoacrylate adhesive composition according to any one of claims 1 to 11, wherein the polyfunctional cyanoacrylate compound has a number average molecular weight of 1,000 to 50,000.
- 前記多官能シアノアクリレート化合物が、ポリオキシアルキレンポリオールの２－シアノアクリル酸エステルを含む、請求項１～請求項１２のいずれか一項に記載の２－シアノアクリレート系接着剤組成物。 The 2-cyanoacrylate adhesive composition according to any one of claims 1 to 12, wherein the polyfunctional cyanoacrylate compound contains a 2-cyanoacrylate ester of polyoxyalkylene polyol.
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| WO2010074095A1 (en) * | 2008-12-25 | 2010-07-01 | 東亞合成株式会社 | Adhesive composition |
| US20170260422A1 (en) * | 2014-09-12 | 2017-09-14 | Afinitica Technologies, S. L. | Fast and elastic adhesive |
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| WO2008056516A1 (en) * | 2006-11-07 | 2008-05-15 | Terumo Kabushiki Kaisha | 2-cyanoacrylate-based adhesive for living organism |
| WO2010074095A1 (en) * | 2008-12-25 | 2010-07-01 | 東亞合成株式会社 | Adhesive composition |
| US20170260422A1 (en) * | 2014-09-12 | 2017-09-14 | Afinitica Technologies, S. L. | Fast and elastic adhesive |
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