JP2005089532A - 2-cyanoacrylate-based adhesive composition - Google Patents
2-cyanoacrylate-based adhesive composition Download PDFInfo
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- JP2005089532A JP2005089532A JP2003321986A JP2003321986A JP2005089532A JP 2005089532 A JP2005089532 A JP 2005089532A JP 2003321986 A JP2003321986 A JP 2003321986A JP 2003321986 A JP2003321986 A JP 2003321986A JP 2005089532 A JP2005089532 A JP 2005089532A
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- Prior art keywords
- cyanoacrylate
- adhesive
- composition
- adhesive composition
- acid
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- 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 47
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 title abstract description 41
- 230000001070 adhesive effect Effects 0.000 title abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 20
- -1 acetyl citric acid triester Chemical class 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000004830 Super Glue Substances 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000005520 cutting process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 3
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 3
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- LVAGMBHLXLZJKZ-UHFFFAOYSA-N 2-o-decyl 1-o-octyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC LVAGMBHLXLZJKZ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-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
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002562 thickening agent Substances 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
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- QCSMHPYITCGSTG-UHFFFAOYSA-N 1-o-butyl 2-o-pentyl benzene-1,2-dicarboxylate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC QCSMHPYITCGSTG-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 1
- IQDPHMACOQAPBQ-UHFFFAOYSA-N 2-ethoxyethyl 2-cyanoprop-2-enoate Chemical compound CCOCCOC(=O)C(=C)C#N IQDPHMACOQAPBQ-UHFFFAOYSA-N 0.000 description 1
- WXAFTQJQXYGOKV-UHFFFAOYSA-N 2-ethylhexyl 2-cyanoprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(=C)C#N WXAFTQJQXYGOKV-UHFFFAOYSA-N 0.000 description 1
- JYTXVMYBYRTJTI-UHFFFAOYSA-N 2-methoxyethyl 2-cyanoprop-2-enoate Chemical compound COCCOC(=O)C(=C)C#N JYTXVMYBYRTJTI-UHFFFAOYSA-N 0.000 description 1
- PFSVSOOFNDBGMO-UHFFFAOYSA-N 3-methoxypropyl 2-cyanoprop-2-enoate Chemical compound COCCCOC(=O)C(=C)C#N PFSVSOOFNDBGMO-UHFFFAOYSA-N 0.000 description 1
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VRKSJXIKRFNNFZ-UHFFFAOYSA-N benzyl 2-cyanoprop-2-enoate Chemical compound N#CC(=C)C(=O)OCC1=CC=CC=C1 VRKSJXIKRFNNFZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- ILRMPAUJTPZAIQ-UHFFFAOYSA-N cyclohexyl 2-cyanoprop-2-enoate Chemical compound N#CC(=C)C(=O)OC1CCCCC1 ILRMPAUJTPZAIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 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
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XDZLHTBOHLGGCJ-UHFFFAOYSA-N hexyl 2-cyanoprop-2-enoate Chemical compound CCCCCCOC(=O)C(=C)C#N XDZLHTBOHLGGCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QRWOVIRDHQJFDB-UHFFFAOYSA-N isobutyl cyanoacrylate Chemical compound CC(C)COC(=O)C(=C)C#N QRWOVIRDHQJFDB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- RPQUGMLCZLGZTG-UHFFFAOYSA-N octyl cyanoacrylate Chemical compound CCCCCCCCOC(=O)C(=C)C#N RPQUGMLCZLGZTG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FNVQIYPKWVVQID-UHFFFAOYSA-N oxolan-2-ylmethyl 2-cyanoprop-2-enoate Chemical compound N#CC(=C)C(=O)OCC1CCCO1 FNVQIYPKWVVQID-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- SXRFXXNXVPFXDU-UHFFFAOYSA-N pentyl 2-cyanoprop-2-enoate Chemical compound CCCCCOC(=O)C(=C)C#N SXRFXXNXVPFXDU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- ITCZEZQMUWEPQP-UHFFFAOYSA-N prop-2-enyl 2-cyanoprop-2-enoate Chemical compound C=CCOC(=O)C(=C)C#N ITCZEZQMUWEPQP-UHFFFAOYSA-N 0.000 description 1
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical compound CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、樹脂型や木型の接着・加工に優れる2−シアノアクリレート系接着剤組成物に関する。 The present invention relates to a 2-cyanoacrylate adhesive composition that is excellent in resin-type and wood-type adhesion and processing.
2−シアノアクリレート系接着剤は、その高いアニオン重合性により、被着体表面や空気中の水分等のアニオン種によって短時間で重合硬化し、各種材料を接着させるため瞬間接着剤として広く用いられている。 2-Cyanoacrylate-based adhesives are widely used as instant adhesives due to their high anionic polymerizability, which are polymerized and cured in a short time by anion species such as adherend surface and moisture in the air to bond various materials. ing.
しかしながら2−シアノアクリレートの硬化物は柔軟性がなく、非常に固い性質を示す。そこで、貼り合わせた後にはみ出した接着剤硬化物を除こうとしても、その硬さから容易に削り取ったりすることができない。 However, the cured product of 2-cyanoacrylate is not flexible and exhibits very hard properties. Then, even if it tries to remove the adhesive hardened | cured material which protruded after bonding together, it cannot remove easily from the hardness.
上記のような問題に対し、これまでに瞬間接着剤に柔軟性を付与し、切削性を向上させようとする試みが行われている。特開平6−329995号には、片方の剤に2−シアノアクリレート組成物を使用した、硬化物の切削性が良好な2剤型充填剤が、特開平11−124522号には、固化物のショア硬度を40〜60に規定した2−シアノアクリレート組成物を木材の補修用として使用することが提案されている。 In the past, attempts have been made to improve the machinability by imparting flexibility to the instantaneous adhesive. Japanese Patent Laid-Open No. 6-329995 discloses a two-part filler using a 2-cyanoacrylate composition as one of the agents and good curability of the cured product, and Japanese Patent Laid-Open No. 11-124522 includes a solidified product. It has been proposed to use a 2-cyanoacrylate composition having a Shore hardness of 40 to 60 for repairing wood.
一方、樹脂型や木型を作製する際の接着に瞬間接着剤が適用できることが特開昭61−23630号等に記載されている。樹脂型や木型というのは、樹脂や合成木材等のブロックを切削、接着し、組み合わせることによって、様々な形態の型を作り出すというものであり、市販されているブロックとしては、バンティコ(株)のレン・シェープや三洋化成工業(株)のサンモジュール等が挙げられる。そして樹脂型や木型を作製するのに、十分な接着強度を有した上で、接着後のはみ出した接着剤硬化物の切削性が良好であると、できあがった型の見栄えが良好となり非常に好まれるのであるが、それと共に瞬間接着剤の硬化性が速すぎず遅すぎないことが、樹脂型や木型の接着加工において極めて重要となる。これは樹脂型や木型は、大きいものでは数メートルになることから、2−シアノアクリレートそのものの硬化性では速すぎて、貼り合わせ後の位置決め等ができないこと。また余りにも遅すぎる場合には、瞬間接着剤としての接着性能が現れないためである。しかしながらこれまでははみ出し部分の切削性と硬化性を両立し、樹脂型や木型の接着・加工に適した2−シアノアクリレート系接着剤は存在しなかった。 On the other hand, Japanese Patent Application Laid-Open No. 61-23630 discloses that an instantaneous adhesive can be applied to bonding when a resin mold or a wooden mold is produced. Resin molds and wooden molds create various types of molds by cutting, adhering, and combining blocks such as resin and synthetic wood. As commercially available blocks, Bantico Co., Ltd. Ren shape and Sanyo Chemical Industries sun module. And when producing resin molds and wooden molds, it has sufficient adhesive strength, and if the adhesive cured product that protrudes after bonding has good machinability, the resulting mold looks very good. Although it is preferred, it is extremely important in the bonding process of resin molds and wooden molds that the curability of the instantaneous adhesive is not too fast and not too slow. This is because the resin mold and the wooden mold are several meters at a large size, so that the curing property of 2-cyanoacrylate itself is too fast and positioning after bonding cannot be performed. Moreover, it is because the adhesive performance as an instantaneous adhesive will not appear when it is too late. However, until now, there has been no 2-cyanoacrylate adhesive suitable for bonding and processing of resin molds and wooden molds, which is compatible with cutting ability and curability of the protruding portion.
本発明の目的は、樹脂型や木型の接着・加工に優れる2−シアノアクリレート系接着剤組成物を提供することにある。 An object of the present invention is to provide a 2-cyanoacrylate-based adhesive composition that is excellent in resin-type and wood-type adhesion and processing.
本発明者らは、2−シアノアクリレートまたは2−シアノアクリレートを主成分とする組成物にある特定のグループから選ばれた可塑化剤を配合すると共に、その配合組成物の酸分を1.0×10-6〜10.0×10-6グラム当量数/gに規定することによって、樹脂型や木型加工後の接着強度が良好な上にはみ出し部分において適度な切削加工性を持たせ、樹脂型・木型を接着する際に位置決め等を行なえる最適な硬化性を有する、樹脂型や木型の接着・加工に最適な2−シアノアクリレート系接着剤組成物が得られることを見出し本発明を完成するに至った。 The inventors of the present invention compounded a plasticizer selected from a specific group in a composition containing 2-cyanoacrylate or 2-cyanoacrylate as a main component, and set the acid content of the compounded composition to 1.0. By prescribing to × 10 −6 to 10.0 × 10 −6 gram equivalent number / g, the adhesive strength after resin mold or wood mold processing is good, and an appropriate cutting workability is given to the protruding portion, It is found that a 2-cyanoacrylate-based adhesive composition that is optimal for bonding and processing of resin molds and wooden molds can be obtained, which has optimal curability that enables positioning and the like when bonding resin molds and wooden molds. The invention has been completed.
ここでいう特定のグループから選ばれた可塑化剤とは、フタル酸エステル、アセチルクエン酸トリエステルおよびアクリロイル基若しくはメタクリロイル基(以下「(メタ)アクリロイル基」と称する。)を有するモノマー若しくはオリゴマーが挙げられ、これらの中の1種または2種以上を使用する。これらの可塑化剤は、多数の可塑化剤の中でも特に十分な接着強度を発揮する上に、更に2−シアノアクリレート接着剤の硬化物の切削性を良好にし本発明の目的に適していることを見出して選択されたものである。 The plasticizer selected from the specific group here is a monomer or oligomer having a phthalate ester, an acetylcitrate triester, and an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”). And one or more of these are used. These plasticizers are particularly suitable for the purpose of the present invention because they exhibit particularly sufficient adhesive strength among many plasticizers and further improve the machinability of the cured product of 2-cyanoacrylate adhesive. Was selected and found.
またこれまでに知られている2−シアノアクリレートを主成分とする組成物の酸分は0.001×10-6〜0.5×10-6グラム当量数/gに抑えられている。これは2−シアノアクリレートがアニオン重合性であることから、酸分が高くなると硬化が遅くなり、瞬間接着剤としての長所を殺してしまうからである。しかしながら、本発明では樹脂型・木型の接着用途には、組成物中の酸分を1.0×10-6〜10.0×10-6グラム当量数/gに規定することが極めて重要だという予想外の知見を得てなされたものである。 Moreover, the acid content of the composition mainly composed of 2-cyanoacrylate known so far is suppressed to 0.001 × 10 −6 to 0.5 × 10 −6 gram equivalent / g. This is because, since 2-cyanoacrylate is anionic polymerizable, the curing becomes slow when the acid content is high, and the advantages as an instantaneous adhesive are killed. However, in the present invention, it is extremely important that the acid content in the composition is defined as 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalent / g for resin-type / wood-type bonding applications. It was made with the unexpected knowledge.
即ち、本発明は2−シアノアクリレートに、フタル酸エステル、アセチルクエン酸トリエステルまたは(メタ)アクリロイル基を有するモノマー若しくはオリゴマーから選ばれた可塑化剤を配合してなる組成物であって、酸分が1.0×10-6〜10.0×10-6グラム当量数/gであることを特徴とする、特に樹脂型や木型の接着・加工に優れる2−シアノアクリレート系接着剤組成物である。 That is, the present invention is a composition comprising 2-cyanoacrylate and a plasticizer selected from a phthalate ester, an acetylcitrate triester, or a monomer or oligomer having a (meth) acryloyl group, A 2-cyanoacrylate adhesive composition particularly excellent in adhesion and processing of resin molds and wooden molds, characterized in that the content is 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalents / g It is a thing.
本発明の2−シアノアクリレート系接着剤組成物は、樹脂型や木型の接着・加工に非常に最適な切削性、硬化性を示すことから、樹脂型や木型用の瞬間接着剤として非常に有用なものである。 The 2-cyanoacrylate-based adhesive composition of the present invention exhibits extremely optimum machinability and curability for bonding and processing of resin molds and wooden molds, so it is very useful as an instantaneous adhesive for resin molds and wooden molds. It is useful for.
以下に、本発明を詳細に説明する。
2−シアノアクリレートは、本発明の接着剤組成物の主成分として用いられるもので、その具体例としては、メチル−2−シアノアクリレート、エチル−2−シアノアクリレート、プロピル−2−シアノアクリレート、イソプロピル−2−シアノアクリレート、ブチル−2−シアノアクリレート、イソブチル−2−シアノアクリレート、アミル−2−シアノアクリレート、ヘキシル−2−シアノアクリレート、シクロヘキシル−2−シアノアクリレート、オクチル−2−シアノアクリレート、2−エチルヘキシル−2−シアノアクリレート、アリル−2−シアノアクリレート、ベンジル−2−シアノアクリレート、メトキシエチル−2−シアノアクリレート、エトキシエチル−2−シアノアクリレート、メトキシプロピル−2−シアノアクリレートおよびテトラヒドロフルフリル−2−シアノアクリレート等が挙げられ、これらの2−シアノアクリレートは1種類にとどまらず2種以上を混合使用することもできる。
The present invention is described in detail below.
2-Cyanoacrylate is used as the main component of the adhesive composition of the present invention. Specific examples thereof include methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, propyl-2-cyanoacrylate, and isopropyl. 2-cyanoacrylate, butyl-2-cyanoacrylate, isobutyl-2-cyanoacrylate, amyl-2-cyanoacrylate, hexyl-2-cyanoacrylate, cyclohexyl-2-cyanoacrylate, octyl-2-cyanoacrylate, 2- Ethylhexyl-2-cyanoacrylate, allyl-2-cyanoacrylate, benzyl-2-cyanoacrylate, methoxyethyl-2-cyanoacrylate, ethoxyethyl-2-cyanoacrylate, methoxypropyl-2-cyanoacrylate Over preparative and tetrahydrofurfuryl 2-cyanoacrylate and the like, these 2-cyanoacrylates may be mixed using two or more not only in one kind.
本発明に用いられる特定のグループから選ばれた可塑化剤の中のうち、フタル酸エステルの具体例としては、フタル酸ジブチル、フタル酸ジエチル、フタル酸ジメチル、フタル酸ジヘプチル、フタル酸ジヘキシル、フタル酸ジn−オクチル、フタル酸ジ−2−エチルヘキシル、フタル酸ジイソノニル、フタル酸オクチルデシル、フタル酸ジイソデシルおよびフタル酸ブチルペンチル等が挙げられ、これらのフタル酸エステル類は1種類にとどまらず2種以上を混合使用することもできる。 Among the plasticizers selected from the specific group used in the present invention, specific examples of the phthalate ester include dibutyl phthalate, diethyl phthalate, dimethyl phthalate, diheptyl phthalate, dihexyl phthalate, phthalate Examples include di-n-octyl acid, di-2-ethylhexyl phthalate, diisononyl phthalate, octyl decyl phthalate, diisodecyl phthalate, and butyl pentyl phthalate. These phthalates are not limited to one type, but two types The above can also be mixed and used.
アセチルクエン酸トリエステルの具体例としては、アセチルクエン酸トリブチル等が挙げられる。 Specific examples of the acetyl citrate triester include tributyl acetyl citrate.
(メタ)アクリロイル基を有するモノマー若しくはオリゴマーの具体例としては、ジ ペンタエリスリトールトリアクリレート、ジペンタエリスリトールテトラアクリレート 、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリ レート、トリメチロールプロパントリアクリレート、エチレングリコールジメタクリレ ート、エチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート 、ポリエチレングリコールジアクリレート、ポリブチルメタクリレートオリゴマー、ポ リメチルアクリレートオリゴマー、ポリエチルアクリレートオリゴマー、ウレタンアク リレートオリゴマーおよびエポキシアクリレートオリゴマー等が挙げられ、これらのモ ノマーまたはオリゴマーは1種類にとどまらず2種以上を混合使用することもできる。 Specific examples of the monomer or oligomer having a (meth) acryloyl group include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate. Examples include methacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polybutyl methacrylate oligomer, polymethyl acrylate oligomer, polyethyl acrylate oligomer, urethane acrylate oligomer, and epoxy acrylate oligomer. One monomer or oligomer of Two or more kinds can be mixed and used.
また、これらフタル酸エステル、アセチルクエン酸トリエステルおよび(メタ)アクリロイル基を有するモノマー若しくはオリゴマーからなるグループの中から2種以上を混合使用することもできる。
これらの3種類の可塑化剤の内、フタル酸エステルおよび(メタ)アクリロイル基を有するモノマー若しくはオリゴマーが、本発明の接着剤組成物の接着強度を良好にするので好ましく、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートが、2−シアノアクリレートと相溶性の良いとの理由から更に好ましい。
また、可塑化剤の配合量は、溶剤を除いた本発明の接着剤組成物中の1〜50質量%が好ましく、更に好ましくは5〜40質量%である。50質量%を超えると接着強度が低くなり、また1質量%未満だと可塑化剤の性能が発揮されずいずれも好ましくない。
Further, two or more of these phthalic acid esters, acetylcitric acid triesters, and monomers or oligomers having a (meth) acryloyl group may be used in combination.
Of these three types of plasticizers, phthalate esters and monomers or oligomers having a (meth) acryloyl group are preferred because they improve the adhesive strength of the adhesive composition of the present invention. Dimethyl phthalate, phthalic acid Diethyl, dibutyl phthalate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are more preferable because they are compatible with 2-cyanoacrylate.
Moreover, 1-50 mass% in the adhesive composition of this invention except the solvent is preferable, and, as for the compounding quantity of a plasticizer, More preferably, it is 5-40 mass%. If it exceeds 50% by mass, the adhesive strength is lowered, and if it is less than 1% by mass, the performance of the plasticizer is not exhibited, which is not preferable.
本発明の2−シアノアクリレート系接着剤組成物は前述の特定の可塑化剤を配合することと、組成物の酸分が1.0×10-6〜10.0×10-6グラム当量数/gに規定することを特徴とするものである。
上記酸分の由来となる酸性成分は、酸性の添加剤、2−シアノアクリレートの加水分解により生じる2−シアノアクリル酸および2−シアノアクリレート製造に用いられる原料の一つであるシアノアセテートの製造段階の加水分解により生じるシアノ酢酸等が挙げられ、本発明はこれらの量を調整することによって組成物の酸分を1.0×10-6〜10.0×10-6グラム当量数/gに調整するものである。
The 2-cyanoacrylate adhesive composition of the present invention contains the above-mentioned specific plasticizer, and the acid content of the composition is 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalent number. / G.
The acidic component derived from the acid content is an acidic additive, 2-cyanoacrylic acid produced by hydrolysis of 2-cyanoacrylate, and a production stage of cyanoacetate which is one of raw materials used for producing 2-cyanoacrylate In the present invention, the acid content of the composition is adjusted to 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalents / g by adjusting these amounts. To be adjusted.
本発明において、2−シアノアクリレート系接着剤組成物中の酸分量は、特開平10−140091号公報において提案された方法を用いて測定されたものである。 In the present invention, the acid content in the 2-cyanoacrylate adhesive composition is measured using the method proposed in JP-A-10-140091.
当該測定方法は、微量の酸分を正確に測定するために、測定時の高温により2−シアノアクリル酸等を分解させる恐れがあるガスクロマトグラフィーによる分析は避け、中和滴定による方法を採用したものであり、更に接着剤の特性を阻害する酸成分のみを正確に把握するために、特定の変色範囲、すなわちpH4.5〜5.0に変色範囲を有する指示薬を用いて中和滴定して求めるものである。
中和滴定の精度を上げるためには、接着剤組成物に水を添加するのがよい。組成物1g当たり蒸留水0.3〜5mlを用いるが、水による2−シアノアクリレートの重合を押さえるためにアセトンやメチルエチルケトン等の有機溶剤を10〜200ml用いることが好ましい。中和滴定の指示薬としては、本発明のように2−シアノアクリレートを主成分とする組成物中の酸分量の測定を目的とする場合には、pH4.5〜5.0の変色範囲を有する指示薬、具体的にはブロモフェノールブルー、2,4−ジニトロフェノール、メチルイエロー等を用いるのが好ましく、ブロモフェノールブルーを用いるのが特に好ましい。中和滴定に用いるアルカリとしては、NaOHまたはKOH水溶液等の強塩基水溶液が用いられ、濃度としては1/10〜1/1000規定が好ましい。
In order to accurately measure a small amount of acid content, the measurement method avoids analysis by gas chromatography, which may decompose 2-cyanoacrylic acid or the like due to high temperature during measurement, and employs a method based on neutralization titration. Furthermore, in order to accurately grasp only the acid component that hinders the properties of the adhesive, neutralization titration is performed using an indicator having a specific color change range, that is, a pH change range of pH 4.5 to 5.0. It is what you want.
In order to increase the accuracy of neutralization titration, it is preferable to add water to the adhesive composition. Although 0.3 to 5 ml of distilled water is used per 1 g of the composition, it is preferable to use 10 to 200 ml of an organic solvent such as acetone or methyl ethyl ketone in order to suppress polymerization of 2-cyanoacrylate by water. The neutralization titration indicator has a color change range of pH 4.5 to 5.0 when the purpose is to measure the amount of acid in a composition containing 2-cyanoacrylate as a main component as in the present invention. An indicator, specifically, bromophenol blue, 2,4-dinitrophenol, methyl yellow or the like is preferably used, and bromophenol blue is particularly preferably used. As the alkali used for the neutralization titration, a strong base aqueous solution such as NaOH or KOH aqueous solution is used, and the concentration is preferably 1/10 to 1/1000.
また本発明の2−シアノアクリレート系接着剤組成物の酸分の調製には酸性の添加剤を使用するのが好ましい。この種類は特に問わないが、特に好ましいのは、配合することによっても2−シアノアクリレートの性質に著しい悪影響を及ぼさないと考えられている二酸化硫黄、スルホン酸誘導体、サルトン酸、三フッ化ホウ素錯体、フッ化ホウ素酸、トリアルキルボレート、カルボン酸誘導体、フェノール性水酸基を有する化合物等が挙げられる。 Moreover, it is preferable to use an acidic additive for the preparation of the acid content of the 2-cyanoacrylate adhesive composition of the present invention. This type is not particularly limited, but particularly preferred is sulfur dioxide, sulfonic acid derivative, sulphonic acid, boron trifluoride complex, which is considered to have no significant adverse effect on the properties of 2-cyanoacrylate even when blended. , Fluorinated boronic acid, trialkylborate, carboxylic acid derivatives, compounds having a phenolic hydroxyl group, and the like.
また本発明の2−シアノアクリレート系接着剤組成物には、通常の2−シアノアクリレート系接着剤に配合させる、硬化促進剤、アニオン重合防止剤、ラジカル重合防止剤、増粘剤、密着性向上剤、揺変剤、着色剤、熱安定剤、軟化剤、充填剤、香料、染料、顔料または溶剤等の各種添加剤を加えてもよい。 In addition, the 2-cyanoacrylate adhesive composition of the present invention is blended with a normal 2-cyanoacrylate adhesive, and includes a curing accelerator, an anionic polymerization inhibitor, a radical polymerization inhibitor, a thickener, and improved adhesion. Various additives such as agents, thixotropic agents, colorants, heat stabilizers, softeners, fillers, fragrances, dyes, pigments or solvents may be added.
硬化促進剤としては、ポリエチレングリコール若しくはその誘導体、クラウンエーテル若しくはその誘導体、カリックスアレーン若しくはその誘導体またはシクロデキストリン若しくはその誘導体等の、2−シアノアクリレートに安定に配合できかつアニオン重合を促進する添加剤が挙げられる。 Examples of the curing accelerator include additives that can be stably added to 2-cyanoacrylate and accelerate anionic polymerization, such as polyethylene glycol or a derivative thereof, crown ether or a derivative thereof, calixarene or a derivative thereof, or cyclodextrin or a derivative thereof. Can be mentioned.
アニオン重合防止剤は、保存容器中の水分等によるアニオン重合を防止する目的で添加され、具体的には二酸化硫黄、芳香族スルホン酸、脂肪族スルホン酸、サルトン酸、三フッ化ホウ素錯体、フッ化ホウ素酸またはトリアルキルボレート等が挙げられる。 An anionic polymerization inhibitor is added for the purpose of preventing anionic polymerization due to moisture or the like in the storage container, and specifically, sulfur dioxide, aromatic sulfonic acid, aliphatic sulfonic acid, sulphonic acid, boron trifluoride complex, fluorine. Examples thereof include boronic acid and trialkylborate.
ラジカル重合防止剤は、貯蔵中の光等によるラジカル重合を防止する目的で添加され、具体的にはハイドロキノンまたはハイドロキノンモノメチルエーテル等が挙げられる。 The radical polymerization inhibitor is added for the purpose of preventing radical polymerization due to light during storage, and specific examples thereof include hydroquinone or hydroquinone monomethyl ether.
増粘剤としては、メタクリル酸エステルやアクリル酸エステルの単独重合若しくは共重合体、ポリスチレン、ポリウレタン、セルロースエステル、エチレン−酢酸ビニル共重合体、エチレン−メタクリル酸エステル共重合体、エチレン−アクリル酸エステル共重合体、アクリロニトリル−アクリルゴム−スチレン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体またはポリ(2−シアノアクリレート)等が挙げられる。 As thickeners, homopolymers or copolymers of methacrylic acid esters and acrylic acid esters, polystyrene, polyurethane, cellulose esters, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid ester copolymers, ethylene-acrylic acid esters Examples include copolymers, acrylonitrile-acrylic rubber-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and poly (2-cyanoacrylate).
また場合によっては、接着剤を塗付する前に、硬化性や接着性を向上させる目的で、ブロックに対してプライマー処理を行なったり、貼り合わせ後、はみ出し部分を硬化させるために硬化剤で後処理することも可能である。 Also, in some cases, before applying the adhesive, a primer treatment is applied to the block for the purpose of improving curability and adhesiveness, and after bonding, a sticking agent is used to harden the protruding portion. It is also possible to process.
本発明は、2−シアノアクリレートに、フタル酸エステル、アセチルクエン酸トリエステルおよび(メタ)アクリロイル基を有するモノマー若しくはオリゴマーのグループの中から選ばれた可塑化剤1種以上を配合すると共に、その配合組成物の酸分を1.0×10-6〜10.0×10-6グラム当量数/gに規定することによって、樹脂型・木型加工後に十分な接着強度を有しつつはみ出し部分において適度な切削加工性を持たせ、樹脂型・木型を接着する際に位置決め等を行なえる最適な硬化性を有する、樹脂型や木型の接着・加工において、従来の2−シアノアクリレート系接着剤にはない極めて最適化された特長を有する。 The present invention blends 2-cyanoacrylate with one or more plasticizers selected from the group of monomers or oligomers having a phthalate ester, an acetylcitrate triester and a (meth) acryloyl group, By regulating the acid content of the blended composition to 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalent number / g, the protruding portion has sufficient adhesive strength after resin mold / wood mold processing In conventional bonding and processing of resin molds and wooden molds, the conventional 2-cyanoacrylate system has appropriate cutting workability and has optimum curability for positioning and the like when bonding resin molds and wooden molds. It has extremely optimized features not found in adhesives.
以下、実施例を挙げて更に詳しく本発明を説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
実施例1〜5、比較例1〜4
表1に記載のように、エチル−2−シアノアクリレートに対して、種々の可塑化剤を添加量を変えて配合し、更にパラトルエンスルホン酸にて酸分が一定量になるように調整した2−シアノアクリレート系接着剤組成物を作製した。そしてこれら接着剤組成物を片方のブロックに塗付し、擦り合わせつつ貼り合わせた。その際の硬化性および切削加工性を測定した。なお基材用のブロックにはバンティコ(株)のレン・シェープ450(ポリウレタン製、接着面積30cm×20cm)を使用した。
Examples 1-5, Comparative Examples 1-4
As shown in Table 1, various plasticizers were added to ethyl-2-cyanoacrylate in various amounts, and further adjusted with paratoluenesulfonic acid so that the acid content was a constant amount. A 2-cyanoacrylate adhesive composition was prepared. Then, these adhesive compositions were applied to one block and bonded together while being rubbed together. The curability and cutting workability at that time were measured. The block for the base material used was Len Shape 450 (manufactured by polyurethane, bonded area 30 cm × 20 cm) manufactured by Bantico Co., Ltd.
なお、酸分測定は次の方法で行った。
(1)200ml容量の三角フラスコに試料3gを精秤する。
(2)この試料に特級アセトンを90ml加え希釈する。
(3)よく振り混ぜた後、蒸留水3ml加える。
(4)指示薬として、ブロモフェノールブルー溶液を数滴加える。
(5)ミクロビュレットを用いて1/100規定のNaOH水溶液を1滴ずつ滴下し、溶液の色が黄色から青色に変わる点を中和終点とする。
The acid content was measured by the following method.
(1) Weigh accurately 3 g of sample into a 200 ml Erlenmeyer flask.
(2) The sample is diluted with 90 ml of special grade acetone.
(3) After shaking well, add 3 ml of distilled water.
(4) Add a few drops of bromophenol blue solution as an indicator.
(5) A 1/100 N aqueous NaOH solution is dropped dropwise using a microburette, and the point at which the color of the solution changes from yellow to blue is defined as the neutralization end point.
また、切削加工性の判定方法は次のとおり。
ブロックを貼り合わせた後にはみ出した接着剤組成物の硬化物に、スプレー式の瞬間接着剤用硬化剤を吹きかけて完全に硬化させた。そして当該硬化物をヤスリで削り取った際の、切削・研磨の容易性について判定した。
Moreover, the judgment method of cutting workability is as follows.
A spray-type curing agent for instant adhesive was sprayed onto the cured adhesive composition that protruded after the blocks were bonded together, and was completely cured. And the ease of cutting and grinding | polishing at the time of scraping off the said hardened | cured material with the file was determined.
また、接着硬化性の測定方法は次のとおり。
ブロックを擦り合わせつつ貼り合わせた後に、接着剤が固化しブロックが動かなくなるまでの時間を測定した。更にその結果に従い、硬化性を判定した。
Moreover, the measuring method of adhesive curability is as follows.
After the blocks were bonded together, the time until the adhesive solidified and the blocks stopped moving was measured. Furthermore, according to the result, curability was determined.
また、接着強度の測定方法はブロックを加工し、JIS-K6861「α−シアノアクリレート系接着剤の試験方法」の引張りせん断接着強さの試験方法に準じて実施した。 In addition, the adhesive strength was measured by processing the block and following the tensile shear bond strength test method of JIS-K6861 “Testing method for α-cyanoacrylate adhesive”.
実施例6〜8、比較例5〜6
表2に記載のように、エチル−2−シアノアクリレートに対して、可塑化剤を一定量添加し、その後パラトルエンスルホン酸にて様々な酸分量になるように調整し、2−シアノアクリレート系接着剤組成物を作製した。そしてこれら接着剤を片方のブロックに塗付し、擦り合わせつつ貼り合わせた。その際の硬化性、切削加工性、接着強度を測定した。なお基材用のブロックには実施例1と同様にバンティコ(株)のレン・シェープ450を使用した。
Examples 6-8, Comparative Examples 5-6
As shown in Table 2, a certain amount of plasticizer was added to ethyl-2-cyanoacrylate, and then adjusted to have various acid contents with para-toluenesulfonic acid. An adhesive composition was prepared. Then, these adhesives were applied to one block and bonded together by rubbing. The curability, cutting workability, and adhesive strength at that time were measured. In the same manner as in Example 1, Len Shape 450 manufactured by Bantico Co., Ltd. was used for the base block.
表1、表2より明らかなように、2−シアノアクリレートに、フタル酸エステル、アセチルクエン酸トリエステルまたは(メタ)アクリロイル基を有するモノマー若しくはオリゴマーから選ばれた可塑化剤を配合させると共に、当該組成物の酸分を1.0×10-6〜10.0×10-6グラム当量数/gに規定することによって、良好な接着強度を有し、型加工後のはみ出し部分において適度な切削加工性を持たせると共に樹脂型や木型を接着する際に位置決め等を行な得る最適な硬化性を有し、樹脂型や木型の接着・加工において、明らかに従来の2−シアノアクリレート系接着剤にはない極めて最適化された加工性を示していることが分かる。
As apparent from Tables 1 and 2, the 2-cyanoacrylate is blended with a plasticizer selected from a phthalate ester, an acetylcitrate triester or a monomer or oligomer having a (meth) acryloyl group, and By regulating the acid content of the composition to 1.0 × 10 −6 to 10.0 × 10 −6 gram equivalent number / g, it has good adhesive strength and is moderately cut at the protruding portion after die processing. It has the best curability to allow positioning and the like when bonding resin molds and wooden molds, and it is clearly the conventional 2-cyanoacrylate system for bonding and processing resin molds and wooden molds. It can be seen that it exhibits extremely optimized processability not found in adhesives.
Claims (1)
A composition comprising 2-cyanoacrylate and a plasticizer selected from a phthalate ester, an acetylcitrate triester, a monomer or an oligomer having an acryloyl group or a methacryloyl group, and having an acid content of 1.0. A 2-cyanoacrylate adhesive composition, wherein the composition is × 10 −6 to 10.0 × 10 −6 gram equivalent / g.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006098438A1 (en) * | 2005-03-18 | 2006-09-21 | Three Bond Co., Ltd. | Cyanoacrylate adhesive composition |
JP2008308647A (en) * | 2007-06-18 | 2008-12-25 | Taoka Chem Co Ltd | 2-cyanoacrylate-based adhesive composition for repairing wood |
EP2039735A4 (en) * | 2006-07-06 | 2014-06-11 | Lintec Corp | Adhesive sheet |
CN113199781A (en) * | 2021-04-30 | 2021-08-03 | 中国人民解放军第五七一九工厂 | Method for repairing rubber pad on lubricating oil tank bracket of aircraft engine |
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JPH06192622A (en) * | 1992-10-08 | 1994-07-12 | Loctite Corp | Heat resistant cyanoacrylate adhesive composition made by using substituted naphthosultone additive |
JPH06329995A (en) * | 1993-05-24 | 1994-11-29 | Alpha Techno Co Ltd | Two-component gap-filling adhesive for making or repairing model |
JPH10140091A (en) * | 1996-11-06 | 1998-05-26 | Toagosei Co Ltd | 2-cyanoacrylate-based adhesive composition |
JP2001164199A (en) * | 1999-12-09 | 2001-06-19 | Taoka Chem Co Ltd | Alpha-cyanoacrylate-based adhesive composition |
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JPH06192622A (en) * | 1992-10-08 | 1994-07-12 | Loctite Corp | Heat resistant cyanoacrylate adhesive composition made by using substituted naphthosultone additive |
JPH06329995A (en) * | 1993-05-24 | 1994-11-29 | Alpha Techno Co Ltd | Two-component gap-filling adhesive for making or repairing model |
JPH10140091A (en) * | 1996-11-06 | 1998-05-26 | Toagosei Co Ltd | 2-cyanoacrylate-based adhesive composition |
JP2001164199A (en) * | 1999-12-09 | 2001-06-19 | Taoka Chem Co Ltd | Alpha-cyanoacrylate-based adhesive composition |
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WO2006098438A1 (en) * | 2005-03-18 | 2006-09-21 | Three Bond Co., Ltd. | Cyanoacrylate adhesive composition |
EP2039735A4 (en) * | 2006-07-06 | 2014-06-11 | Lintec Corp | Adhesive sheet |
JP2008308647A (en) * | 2007-06-18 | 2008-12-25 | Taoka Chem Co Ltd | 2-cyanoacrylate-based adhesive composition for repairing wood |
CN113199781A (en) * | 2021-04-30 | 2021-08-03 | 中国人民解放军第五七一九工厂 | Method for repairing rubber pad on lubricating oil tank bracket of aircraft engine |
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