JPS624431B2 - - Google Patents
Info
- Publication number
- JPS624431B2 JPS624431B2 JP52109104A JP10910477A JPS624431B2 JP S624431 B2 JPS624431 B2 JP S624431B2 JP 52109104 A JP52109104 A JP 52109104A JP 10910477 A JP10910477 A JP 10910477A JP S624431 B2 JPS624431 B2 JP S624431B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- adhesive composition
- composition according
- bis
- adhesive strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000001070 adhesive effect Effects 0.000 claims description 184
- 239000000853 adhesive Substances 0.000 claims description 182
- 239000000203 mixture Substances 0.000 claims description 62
- 229920001577 copolymer Polymers 0.000 claims description 31
- -1 polymethylene Polymers 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000004816 latex Substances 0.000 claims description 14
- 229920000126 latex Polymers 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 150000002689 maleic acids Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004069 aziridinyl group Chemical group 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- GSKNOMRGZLSYCL-UHFFFAOYSA-N penta-1,4-dien-3-imine Chemical compound C=CC(=N)C=C GSKNOMRGZLSYCL-UHFFFAOYSA-N 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 239000000306 component Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 23
- 239000002585 base Substances 0.000 description 22
- 238000009835 boiling Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000002023 wood Substances 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000011976 maleic acid Substances 0.000 description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 9
- 239000011120 plywood Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000011121 hardwood Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- RRZJBIGIFWXZCO-UAIGNFCESA-N C(\C=C/C(=O)O)(=O)O.C1(\C=C/C(=O)O1)=O.CC(C)=C Chemical compound C(\C=C/C(=O)O)(=O)O.C1(\C=C/C(=O)O1)=O.CC(C)=C RRZJBIGIFWXZCO-UAIGNFCESA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- YVOQADGLLJCMOE-UHFFFAOYSA-N n-[6-(aziridine-1-carbonylamino)hexyl]aziridine-1-carboxamide Chemical compound C1CN1C(=O)NCCCCCCNC(=O)N1CC1 YVOQADGLLJCMOE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ZCSHACFHMFHFKK-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;2,4,6-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)C1NC([N+]([O-])=O)NC([N+]([O-])=O)N1.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZCSHACFHMFHFKK-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HZGSQPAPBIIIDM-UHFFFAOYSA-N furan-2,5-dione hydrate Chemical compound O.C1(C=C/C(=O)O1)=O HZGSQPAPBIIIDM-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 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
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は新規な水性接着剤組成物に関し、その
目的とするところは中性領域且つ室温に於て短時
間圧締で接着し、短時間養生で硬化して優れた常
態接着力、耐水接着力、耐熱接着力、耐煮沸繰返
し接着力、耐久接着力、耐衝撃接着力等の諸性能
を発揮し得る水性接着剤組成物を提供することに
ある。
木材又は木質材料と異質材料間の接着に於てそ
れぞれ同志又は相互を組み合わせて屋内用又は屋
外用途の合板、木質パネル、複合材パネル、集成
材、二次加工合板等を製造するために今日まで
種々の接着剤が開発されている。従来上記用途に
は縮合系樹脂接着剤、ポリ酢酸ビニル樹脂系接着
剤、α−オレフイン−無水マレイン酸共重合体系
接着剤等を接着時の作業条件、接着剤の使途によ
り要求される性能等に応じて使用されている。し
かし乍らこれら接着剤は、(1)室温接着が可能なこ
と、(2)室温硬化性を有すること、(3)実用上充分な
可使時間を有すること、(4)優れた常態接着力、耐
水接着力、耐熱接着力、耐煮沸繰返し接着力、耐
久接着力、耐衝撃接着力等の接着性能を有するこ
と、(5)接着剤のPHが中性領域にあり且つホルマリ
ン、溶剤等を含有せず安全に使用し得ること、(6)
接着剤の塗付作業後塗付機械の水洗が容易で作業
性が良好であること等の諸性質を全て具備するも
のではない。而して上記使途に対してより有効に
且つ経済的に使い得る接着剤としてこれら諸性質
の全てを満足し得る接着剤組成物の出現が強く望
まれている。
本発明者らは斯かる現状に鑑みこれら接着剤組
成物のうちα−オレフイン−無水マレイン酸共重
合体接着剤に関して改良を試みた。α−オレフイ
ン−無水マレイン酸共重合体を含有する接着剤に
はカルボキシル基が親水性であるために耐水接着
力、耐煮沸繰返し接着力等の接着力が劣るばかり
か耐久接着力、耐衝撃接着力も劣るという重大な
欠点があり、特公昭49−47892号、特開昭48−
42032号、特開昭48−91136号、特開昭49−25027
号、特開昭50−109229号等に記載されている如く
α−オレフイン−無水マレイン酸共重合体に多価
金属水酸化物もしくは酸化物、ポリエチレンイミ
ン等のカチオン性高分子電解質等を配合する試み
がなされている。しかしながら斯かる化合物を配
合した接着剤は単にカルボキシル基に対しイオン
的結合又はキレート形成する程度のものであり、
従つて斯かる接着剤を用いて処理しても耐水接着
力、耐熱接着力、耐煮沸繰返し接着力、耐久接着
力、耐衝撃接着力等は僅かしか向上せず優れた性
能が発揮され得ない。斯かる接着剤組成物の性能
を更に改良すべくエポキシ化合物、ジイソシアネ
ート類等の架橋性化合物を添加配合する試みもな
されている。しかしながらこの種架橋性化合物を
添加配合して得られる接着剤組成物にも種々の欠
点がある。例えばジイソシアネート類を添加配合
した接着剤組成物は室温硬化性を有さず加熱硬化
させるために種々の問題が生ずる。即ち接着され
るべき基材を加熱しなければならない為に加熱装
置及び付帯装置等の多大な設備を必要とし、加熱
により基材寸法に狂いが生じたり、接着時の基材
の圧締枚数が制限されると同時に基材の厚みが厚
い場合には熱伝導性が悪く硬化が不充分となり従
つて接着不良が発生したり、また使用される基材
によつては加熱により変色する危険性がある等の
難点がある。しかもジイソシアネート類を添加配
合した接着剤を加熱硬化させる際にイソシアネー
ト基とカルボキシル基とが脱炭酸反応して気泡が
発生し接着性が低下するのを避け得ず、従つて硬
化させて得られる製品の耐水接着力、耐熱接着
力、耐煮沸繰返し接着力、耐久接着力、耐衝撃接
着力等の諸性能は極めて悪く実用性に乏しい。ま
たエポキシ化合物を添加配合した接着剤組成物は
一般に加熱硬化型のものであり、前記ジイソシア
ネート類配合の接着剤組成物と同様の欠点を有
し、しかも硬化させて得られる製品の諸性能は充
分満足し得るものではない。斯かるエポキシ化合
物配合の接着剤組成物は室温にて硬化はするが、
硬化させて得られる製品の諸性能はエポキシ化合
物を配合しない組成物を用いて得られる製品のそ
れに比し若干向上するのみであつて実用的に使用
し得るものでは全くない。斯かる接着剤組成物に
苛性ソーダ等の強塩基や消石灰等の多価金属水酸
化物を加えてPH12以上の強アルカリ性にすれば室
温にて硬化させて得られる製品の耐水接着力、耐
熱接着力、耐煮沸繰返し接着力、耐久接着力、耐
衝撃接着力等の諸性能はある程度向上するが、そ
れでもなお不充分であり実用性に乏しい。しかも
斯かる強アルカリ領域にて該組成物を接着させる
際に基材特に木材が著しく汚染されると共に木材
表面の脆化を生じ従つて得られる接着製品の品質
的価値を低下させるという難点があり、また斯か
る難点のために薄物材料の貼合せが不適当である
など使用用途が限られる傾向にある。更に強アル
カリ領域にて接着作業を行なう際強アルカリの為
人体に対して危険である、塗付機械等を洗浄して
生ずる廃水を中和処理しなければならない等の難
点も無視し得ない。
このように樹脂成分としてα−オレフイン−無
水マレイン酸共重合体を配合した接着剤組成物で
あつて、中性領域にて室温硬化ししかも短時間圧
締、短時間養生にて優れた常態接着力、耐水接着
力、耐熱接着力、耐煮沸繰返し接着力、耐久接着
力、耐衝撃接着力等高度の諸性能を発揮し得る組
成物は今日まで全く知られていない。更に斯かる
接着剤は硬化反応の温度依存性が大きく従つて温
度の高い夏季期間では可使時間が極端に短かくな
ることにより制約が加えられ、一方温度の低い冬
季期間では硬化反応の遅延により圧締及び養生時
間を長くする必要がある等作業性や接着剤の品質
管理の点で問題を有していた。
本発明者らは斯かる現状に鑑み中性領域にて室
温硬化し、短時間圧締、短時間養生にて高度の諸
性能を発揮し得、しかも実用上充分な可使時間を
有する接着剤組成物を開発すべく鋭意研究を続け
てきた。その研究過程において、α−オレフイン
とマレイン酸類との共重合体の部分もしくは完全
中和物に、分子内に２個以上のアジリジン環を有
する化合物を配合した組成物を用いて、ラワン系
合板同志を接着、即ち再合板を作成して接着性能
を評価したところ、ほぼ満足できる結果が得られ
ることを見い出した。
しかるに、斯かる合板は薄単板を相互に直交さ
せて積層接着させたものであるから、寸法変化が
極めて少ないことが知られており、しかも表面材
料が軟弱な南洋材の為、接着破壊試験時に木破を
生じ易く、接着層間の本来の接着力は判別し難い
傾向にある。そこで硬く寸法変化が激しく木破を
生じ難い、即ち本来の接着力を判別し易い広葉樹
材を、上記の組成物を用いて接着し、JIS Ｋ
6852によるブロツク圧縮せん断試験により各種性
能を評価したところ、耐水、耐温水、耐煮沸繰返
し強度等が不充分であることが判明した。これ
は、材が硬く木破を生じ難い為に、本来の接着層
に関係した強度が得られ、しかも単一材の為合板
に比べて寸法変化が大きく、各種試験条件下で接
着物に過大な応力がかかり、接着層が急激に劣化
したことによるものと考えられる。また、一方の
被着体が寸法変化の少ない合板であつても、片方
が広葉樹材であれば上記各種性能が不充分である
ことも判明した。
そこで広葉樹材同志の接着にも、優れた耐水接
着力、耐温水接着力、耐煮沸繰返し接着力等を発
現し得る接着剤組成物を開発すべく研究を重ねた
ところ、α−オレフイン、マレイン酸類及びマレ
イン酸イミド類の共重合体の部分もしくは完全中
和物に、分子内に２個以上のアジリジン環を有す
る化合物を配合した組成物が、本発明の所期の目
的を達成し得ることを見い出し、ここに本発明を
完成するに至つた。
即ち、本発明は、
(a) α−オレフイン、マレイン酸類及びマレイン
酸イミド類の共重合体の部分もしくは完全中和
物、及び
(b) 分子内に２個以上のアジリジン環を有する化
合物
を含有せしめてなる水性接着剤組成物に係る。
本発明組成物は中性領域にて室温で更には低温
でも硬化し、短時間圧締、短時間養生にて優れた
常態接着力、耐水接着力、耐熱接着力、耐煮沸繰
返し接着力、耐久接着力、耐衝撃接着力等高度の
諸性能を発揮し得、しかも実用上充分な可使時間
を有し且つ安全に使用し得るものであり、従来の
この種接着剤の欠点を悉く解消し得るものであ
る。
即ち本発明組成物は中性領域にて室温硬化する
ものであり、従つて(1)木材その他熱伝導度の低い
材料の接着が容易となり且つ形状や寸法の異なる
フラツシユパネル等の製造も可能となり、多品種
製品の製造が可能になる、(2)加熱による製品の反
りや狂いが生じず製品の品質を向上し得不良率を
減少し得る、(3)加熱装置及び付帯装置等の多大な
設備を必要とせず、また１プレス工程当りの積み
上げ枚数の増加により量産化が可能となり、製品
コストを減少し得る、(4)中性領域で行ない得るの
で、木材汚染がなく製品の品質的価値を低下させ
ることはなく、また人体に害を及ぼしたり衣服を
損傷したりすることがなく、また廃水処理を容易
に施し得る等の利点を有する。また本発明組成物
は短時間圧締、短時間養生により高性能を発揮し
得るものであり、従つて(5)作業能率及び製品の品
質を向上し得る、(6)製造後直ちに出荷できるだけ
でなく万一製品を炎天、降雨など屋外の悪条件に
さらしても剥離する必配がなく、厳しい使用条件
が必要とされる屋外など広範囲の用途に適用し得
る、(7)硬く寸法変化が激しく木破を生じ難い広葉
樹材同志の接着にも、優れた耐水接着力、耐温水
接着力、耐煮沸繰返し接着力等を発現し得る等の
利点を有する。更に樹脂成分として配合された共
重合体の中和度を調整することにより実用上充分
な可使時間を賦与でき作業性を向上し得る。
本発明では樹脂成分としてα−オレフイン、マ
レイン酸類及びマレイン酸イミド類の共重合体の
部分もしくは完全中和物が使用される。α−オレ
フインとはα−位に二重結合を有するオレフイン
系不飽和化合物を意味し、公知のものを広く使用
し得る。これらのうちでも炭素数２〜８の直鎖状
もしくは分岐状脂肪族系α−オレフイン、例えば
エチレン、プロピレン、ｎ−ブテン、イソブチレ
ン、ｎ−ペンテン、２−メチル−１−ブデン、ｎ
−ヘキセン、２−メチル−１−ペンテン、３−メ
チル−１−ペンテン、４−メチル−１−ペンテ
ン、２−エチル−１−ブテン等が好ましい。この
うちでもイソブチレンが特に好ましい。またここ
でイソブチレンとはイソブチレンを含むリターン
BBをも意味する。これらα−オレフインは単独
で用いてもよいし２種以上用いてもよい。またマ
レイン酸類とは無水マレイン酸及びマレイン酸を
意味し、マレイン酸イミド類とはマレイン酸イミ
ド及びＮ−置換マレイン酸イミドを意味する。Ｎ
−置換マレイン酸イミドはマレイン酸イミドを構
成する窒素原子に結合した水素原子を適当な置換
基で置換して得られるもので、置換基としてはア
ルキル、フエニルヒドロキシアルキル、ヒドロキ
シフエニル、カルボキシアルキル、カルボキシフ
エニル、第１級アミノアルキル、第２級アミノア
ルキル、第３級アミノアルキル基等が包含され
る。本発明で使用されるα−オレフイン、マレイ
ン酸類及びマレイン酸イミド類の共重合体（以下
「共重合体Ａ」と記す）は上記モノマーを適宜組
み合わせて常法に従つて製造されるものである。
共重合体Ａを構成するモノマー成分であるマレイ
ン酸類の一部をマレイン酸モノまたはジアルキル
エステル、マレイン酸モノまたはジアリルエステ
ル、マレイン酸モノまたはジアラルキルエステ
ル、マレイン酸モノまたはジシクロエステル、マ
レイン酸モノまたはジシクロアルキルエステル等
のマレイン酸モノまたはジエステルに置き換えて
もよく、また共重合体Ａの一部をアルコール変性
してもよい。共重合体Ｂは共重合体Ａを所望のマ
レイン酸イミド構造もしくはＮ−置換マレイン酸
イミド構造を与える適当な窒素化合物と反応させ
ることによつても製造される。斯かる窒素化合物
としてはアンモニア、第１級脂肪族アミン、芳香
族アミン、ヒドロキシアルキルアミン、アミノフ
エノール、脂肪族アミノカルボン酸、ラクタム、
芳香族アミノカルボン酸、脂肪族ジアミン、Ｎ−
置換脂肪族アミン、Ｎ，Ｎ−置換脂肪族ジアミン
等を例示し得る。代表的製法を示せば、以下の通
りである。即ち、α−オレフインと無水マレイン
酸との共重合体を脱水後、不活性有機溶媒に懸濁
又は溶解し、アンモニアガスを作用させてアミド
アンモニウム塩とする。一旦その塩を形成後、脱
水状態で130℃以上の高温で加熱する。この加熱
は、160〜180℃の範囲が好ましい。この場合イミ
ド化の促進を図る為、乾燥アンモニアガスを吹き
込んでもよい。この製法において、アンモニアの
代りに上記窒素化合物を使用すれば、アミドアミ
ン塩が形成され、これを脱水状態で加熱すればイ
ミド化物を得ることができる。該製法において
は、イミド化反応での加熱工程で水分が存在すれ
ば、イミド化物の加水分解を生じるので、脱水状
態を保つ必要がある。共重合体Ａを構成するα−
オレフイン、マレイン酸類及びマレイン酸イミド
類の比率は一般にモル比でα−オレフイン：（マ
レイン酸類＋マレイン酸イミド類）＝１：0.8〜
1.2、好ましくはほぼ１：１であり且つマレイン
酸類：マレイン酸イミド類＝0.9〜0.3：0.1〜
0.7、好ましくは0.8〜0.4：0.2〜0.6であるのがよ
い。マレイン酸類の比率がα−オレフインに比べ
て極端に少なくなると、水性接着剤を得るのが困
難な傾向となり、接着力特に常態耐水接着力、耐
熱接着力が低下する傾向となる。マレイン酸類の
比率がα−オレフインに比べて極端に多くなる
と、耐水接着力、耐衝撃接着力が低下する傾向と
なる。マレイン酸イミド類の量が極端に多くなる
と水性接着剤を得るのが困難な傾向となる。共重
合体Ａの重合度としては特に限定されないが、通
常200〜10000程度が適当である。重合度が200よ
り極端に小さいと塗工性等の作業性が低下してく
る傾向になると共に接着性能の低下を来たす傾向
となる。また逆に重合度が10000より極端に大き
くなつても上記と同様の傾向が生ずる。本発明に
おいては共重合体Ａの重合度が400〜5000の範囲
内にあるのが好ましい。
本発明では上記共重合体Ａの部分もしくは完全
中和物（以下「(a)成分」と記す）が使用される。
共重合体Ａの中和度としては一般に共重合体中の
全カルボキシル基数の30モル％以上、好ましくは
40モル％以上中和されているのがよい。全カルボ
キシル基数とはマレイン酸部分のカルボキシル基
と無水マレイン酸部分の酸無水物基１個をカルボ
キシル基２個と換算したものとを合計したもので
ある。中和度が30モル％に満たない(a)成分を配合
して得られる接着剤組成物は短時間の内に架橋し
増粘またはゲル化により塗工程が低下したり、ゲ
ル化に基づいた濡れ現象の低下を招いて接着不良
の原因となる等好ましいものではない。中和度が
小さい(a)成分を配合して得られる接着剤組成物は
一般に可使時間が比較的短く硬化速度は比較的速
い。また中和度が大きい(a)成分を配合して得られ
る接着剤組成物は一般に可使時間が比較的長く硬
化速度は比較的遅い。従つて接着剤組成物の使途
に応じて可使時間及び硬化速度が所望のものとな
るように(a)成分の中和度を適宜選択すればよい。
(a)成分は共重合体Ａに中和剤を反応させることに
より得られる。斯かる中和剤としては特に限定が
なく公知の塩基性化合物を広く使用することがで
き、具体的にはアンモニア（アンモニア水）、ア
ンモニアの炭酸塩、燐酸塩もしくは酢酸塩、モノ
エタノールアミン、ジエタノールアミン、トリエ
タノールアミン、その他のアルキロールアミン、
脂肪族アミン、芳香族アミン等の有機アミン類、
アルカリ土類金属の酸化物、水酸化物もしくは炭
酸塩、アルカリ金属の水酸化物、炭酸塩、珪酸
塩、燐酸塩、酢酸塩等の弱酸塩を例示できる。こ
れらのうちでアンモニア、アンモニアの炭酸塩、
有機アミン類及びアルカリ土類金属の酸化物、水
酸化物もしくは炭酸塩がより好ましい。中和剤の
使用量としては特に限定されないが、中和度が30
モル％以上となり且つ(a)成分を配合して得られる
接着剤組成物のPHが４〜10の範囲内になるような
量を使用するのが好ましい。PHが４より小さくな
ると酸成分により架橋が促進され増粘またはゲル
化により塗工程が低下したり接着性が低下する傾
向となる。またPHが10を越えると室温硬化性に乏
しくなる傾向となる。
斯かる(a)成分を配合して得られる接着剤組成物
は室温硬化性に優れ冬期の低温期（５〜10℃）に
於ても一層短時間圧締による速硬化性が得られる
と同時に短期養生にて著しく優れた常態接着力、
耐水接着力、耐熱接着力、耐煮沸繰返し接着力、
耐久接着力、耐衝撃接着力等高度の諸性能が発現
される。マレイン酸イミド類としてマレイン酸イ
ミドを導入するのが最も好ましい。
本発明に於て使用される分子内に２個以上のア
ジリジン環を有する化合物（以下「(b)成分」とい
う）としては分子内に基
The present invention relates to a novel water-based adhesive composition, the purpose of which is to provide adhesive in a neutral region and at room temperature by short pressing, cure after short curing, and exhibit excellent normal adhesive strength and water-resistant adhesive strength. It is an object of the present invention to provide an aqueous adhesive composition that can exhibit various performances such as heat-resistant adhesive strength, boiling-resistant repeated adhesive strength, durable adhesive strength, and impact-resistant adhesive strength. To date, the use of adhesives between wood or wood-based materials and dissimilar materials to produce plywood, wood-based panels, composite panels, laminated wood, secondary processed plywood, etc. for indoor or outdoor use by combining them with each other or with each other. Various adhesives have been developed. Conventionally, condensation resin adhesives, polyvinyl acetate resin adhesives, α-olefin-maleic anhydride copolymer adhesives, etc. have been used for the above applications, depending on the performance required depending on the working conditions at the time of bonding and the intended use of the adhesive. used accordingly. However, these adhesives must (1) be capable of adhesion at room temperature, (2) have room temperature curability, (3) have a practically sufficient pot life, and (4) have excellent normal adhesive strength. , have adhesive properties such as water resistant adhesive strength, heat resistant adhesive strength, repeated boiling resistant adhesive strength, durable adhesive strength, impact resistant adhesive strength, etc. (5) The pH of the adhesive is in the neutral range and is free from formalin, solvents, etc. Contains no substances and can be used safely; (6)
It does not have all the properties such as easy washing of the coating machine with water after applying the adhesive and good workability. Therefore, there is a strong desire for an adhesive composition that can satisfy all of these properties as an adhesive that can be used more effectively and economically for the above uses. In view of the current situation, the present inventors attempted to improve the α-olefin-maleic anhydride copolymer adhesive among these adhesive compositions. Adhesives containing α-olefin-maleic anhydride copolymer have hydrophilic carboxyl groups, so they not only have inferior adhesive strength such as water resistant adhesive strength and repeated boiling resistant adhesive strength, but also have poor adhesive strength such as durable adhesive strength and impact resistant adhesive strength. It has the serious drawback of being inferior in power, and is
No. 42032, JP-A-48-91136, JP-A-49-25027
As described in JP-A-50-109229, etc., a polyvalent metal hydroxide or oxide, a cationic polymer electrolyte such as polyethyleneimine, etc. are blended with an α-olefin-maleic anhydride copolymer. Attempts are being made. However, adhesives containing such compounds merely form ionic bonds or chelates with carboxyl groups;
Therefore, even if treated with such an adhesive, water resistant adhesive strength, heat resistant adhesive strength, repeated boiling resistant adhesive strength, durable adhesive strength, impact resistant adhesive strength, etc. are only slightly improved, and excellent performance cannot be exhibited. . In order to further improve the performance of such adhesive compositions, attempts have been made to add crosslinking compounds such as epoxy compounds and diisocyanates. However, adhesive compositions obtained by adding and blending this type of crosslinkable compound also have various drawbacks. For example, adhesive compositions containing diisocyanates do not have room temperature curability and are cured by heating, which causes various problems. In other words, since the base materials to be bonded must be heated, a large amount of equipment such as a heating device and ancillary equipment is required, and heating may cause deviations in the dimensions of the base materials or reduce the number of substrates to be pressed during bonding. At the same time, if the base material is thick, thermal conductivity may be poor and curing may be insufficient, resulting in poor adhesion, and depending on the base material used, there is a risk of discoloration due to heating. There are some difficulties. Furthermore, when an adhesive containing diisocyanates is heat-cured, the isocyanate group and the carboxyl group undergo a decarboxylation reaction, generating bubbles and reducing adhesive properties. Its various properties such as water-resistant adhesive strength, heat-resistant adhesive strength, boiling-resistant repeated adhesive strength, durable adhesive strength, and impact-resistant adhesive strength are extremely poor, making it impractical. Furthermore, adhesive compositions containing epoxy compounds are generally heat-curable and have the same drawbacks as the adhesive compositions containing diisocyanates, but the performance of the products obtained by curing them is sufficient. It's not something I'm satisfied with. Although adhesive compositions containing such epoxy compounds cure at room temperature,
The performance of the product obtained by curing is only slightly improved compared to that of a product obtained using a composition that does not contain an epoxy compound, and cannot be used practically at all. If a strong base such as caustic soda or a polyvalent metal hydroxide such as slaked lime is added to such an adhesive composition to make it strong alkaline with a pH of 12 or higher, the water-resistant adhesive strength and heat-resistant adhesive strength of the product obtained by curing at room temperature can be improved. Although various performances such as repeated boiling adhesive strength, durable adhesive strength, and impact resistant adhesive strength are improved to some extent, they are still insufficient and lack practical use. Moreover, when adhering the composition in such a strong alkaline region, there is a problem in that the base material, especially wood, is significantly contaminated and the surface of the wood becomes brittle, thus reducing the quality value of the resulting adhesive product. Moreover, due to such drawbacks, the applications tend to be limited, such as making it inappropriate to bond thin materials together. Furthermore, when bonding work is performed in a strongly alkaline area, the strong alkali is dangerous to the human body, and the disadvantages of having to neutralize the waste water generated by cleaning the coating machine etc. cannot be ignored. This adhesive composition contains α-olefin-maleic anhydride copolymer as a resin component, and it cures at room temperature in a neutral region, and has excellent normal adhesion after short pressing and short curing. To date, no composition has been known that can exhibit high performance such as strength, water-resistant adhesive strength, heat-resistant adhesive strength, repeated boiling adhesive strength, durable adhesive strength, and impact-resistant adhesive strength. Furthermore, the curing reaction of such adhesives is highly temperature dependent, and is therefore limited by extremely short pot life in the hot summer months, while in the cold winter months, the curing reaction is delayed. There were problems in terms of workability and quality control of the adhesive, such as the need for long clamping and curing times. In view of the current situation, the present inventors have developed an adhesive that cures at room temperature in a neutral region, can exhibit high performance with short pressing and curing, and has a pot life long enough for practical use. We have been conducting intensive research to develop the composition. In the course of this research, we used a composition in which a partially or completely neutralized copolymer of α-olefin and maleic acids was blended with a compound having two or more aziridine rings in the molecule. When we evaluated the adhesion performance by gluing (that is, re-plywood), we found that almost satisfactory results were obtained. However, since such plywood is made by laminating and bonding thin veneers perpendicular to each other, it is known that dimensional changes are extremely small.Furthermore, since the surface material is soft South Sea wood, it is difficult to conduct adhesive failure tests. Sometimes wood breaks easily occur, and the original adhesive strength between the adhesive layers tends to be difficult to discern. Therefore, we used the above composition to bond hardwood materials that are hard, have large dimensional changes, are hard to cause wood breakage, and therefore have easy-to-determine original adhesion strength, and adhered to JIS K
When various performances were evaluated using a block compression shear test using 6852, it was found that water resistance, hot water resistance, boiling cyclic strength, etc. were insufficient. This is because the material is hard and does not easily break, so the strength related to the original adhesive layer can be obtained.Moreover, because it is a single material, dimensional changes are larger than that of plywood, and under various test conditions This is thought to be due to the rapid deterioration of the adhesive layer due to the stress applied. It has also been found that even if one of the adherends is made of plywood with little dimensional change, the above-mentioned various performances are insufficient if the other is made of hardwood. Therefore, we conducted repeated research to develop an adhesive composition that can exhibit excellent water-resistant adhesive strength, hot water-resistant adhesive strength, and repeated boiling-resistant adhesive strength for adhesion between hardwood materials. It has been found that a composition containing a partially or completely neutralized copolymer of maleic acid imides and a compound having two or more aziridine rings in the molecule can achieve the intended purpose of the present invention. This heading has led us to complete the present invention. That is, the present invention provides (a) a partially or completely neutralized product of a copolymer of α-olefin, maleic acids, and maleic acid imides, and (b) a compound containing two or more aziridine rings in the molecule. The present invention relates to an aqueous adhesive composition. The composition of the present invention cures at room temperature and even at low temperatures in a neutral region, and has excellent normal adhesive strength, water-resistant adhesive strength, heat-resistant adhesive strength, boiling-resistant repeated adhesive strength, and durability even after short-time pressing and short-time curing. It is able to exhibit high-level performance such as adhesive strength and impact-resistant adhesive strength, has a pot life long enough for practical use, and is safe to use, eliminating all the shortcomings of conventional adhesives of this type. It's something you get. That is, the composition of the present invention cures at room temperature in a neutral region, and therefore (1) it is easy to bond wood and other materials with low thermal conductivity, and it is also possible to manufacture flash panels with different shapes and dimensions. This makes it possible to manufacture a wide variety of products, (2) improves product quality without causing product warping or deformation due to heating, and reduces defective rates; (3) reduces the need for heating equipment and auxiliary equipment, etc. (4) Since the process can be carried out in a neutral region, there is no wood contamination and the quality of the product is improved. It has the advantage that it does not reduce its value, does not cause harm to the human body or damage clothing, and can be easily treated as waste water. In addition, the composition of the present invention can exhibit high performance through short-time compaction and short-time curing, so (5) it can improve work efficiency and product quality, and (6) it can be shipped immediately after manufacturing. (7) It is hard and does not cause dimensional changes. It also has the advantage of exhibiting excellent water-resistant adhesive strength, hot water-resistant adhesive strength, repeated boiling-resistant adhesive strength, etc. for adhesion of hardwood materials that do not easily cause wood breakage. Furthermore, by adjusting the degree of neutralization of the copolymer blended as a resin component, a practically sufficient pot life can be imparted and workability can be improved. In the present invention, a partially or completely neutralized copolymer of α-olefin, maleic acids, and maleic acid imides is used as the resin component. α-olefin means an olefinic unsaturated compound having a double bond at the α-position, and a wide variety of known compounds can be used. Among these, linear or branched aliphatic α-olefins having 2 to 8 carbon atoms, such as ethylene, propylene, n-butene, isobutylene, n-pentene, 2-methyl-1-butene, n
-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene and the like are preferred. Among these, isobutylene is particularly preferred. Also, isobutylene here refers to return containing isobutylene.
It also means BB. These α-olefins may be used alone or in combination of two or more kinds. Furthermore, maleic acids mean maleic anhydride and maleic acid, and maleic imides mean maleic imide and N-substituted maleic imide. N
-Substituted maleic acid imide is obtained by substituting the hydrogen atom bonded to the nitrogen atom constituting maleic acid imide with an appropriate substituent, and the substituent is alkyl, phenylhydroxyalkyl, hydroxyphenyl, carboxyalkyl. , carboxyphenyl, primary aminoalkyl, secondary aminoalkyl, tertiary aminoalkyl, and the like. The copolymer of α-olefin, maleic acid, and maleic acid imide (hereinafter referred to as "copolymer A") used in the present invention is produced by appropriately combining the above monomers according to a conventional method. .
A part of the maleic acids which are the monomer components constituting copolymer A can be substituted with maleic acid mono- or dialkyl ester, maleic acid mono- or diallyl ester, maleic acid mono- or diallkyl ester, maleic acid mono- or dicycloester, or maleic acid mono- or di-alkyl ester. Alternatively, it may be replaced with maleic acid mono- or diester such as dicycloalkyl ester, or a part of copolymer A may be modified with alcohol. Copolymer B is also prepared by reacting copolymer A with a suitable nitrogen compound that provides the desired maleimide or N-substituted maleimide structure. Such nitrogen compounds include ammonia, primary aliphatic amines, aromatic amines, hydroxyalkylamines, aminophenols, aliphatic aminocarboxylic acids, lactams,
Aromatic aminocarboxylic acids, aliphatic diamines, N-
Examples include substituted aliphatic amines and N,N-substituted aliphatic diamines. A typical manufacturing method is as follows. That is, after a copolymer of α-olefin and maleic anhydride is dehydrated, it is suspended or dissolved in an inert organic solvent and treated with ammonia gas to form an amide ammonium salt. Once the salt is formed, it is heated in a dehydrated state at a high temperature of 130°C or higher. This heating is preferably in the range of 160 to 180°C. In this case, dry ammonia gas may be blown in to promote imidization. In this production method, if the above nitrogen compound is used instead of ammonia, an amidoamine salt is formed, and if this is heated in a dehydrated state, an imidide can be obtained. In this production method, if moisture is present during the heating step in the imidization reaction, hydrolysis of the imidide will occur, so it is necessary to maintain a dehydrated state. α- constituting copolymer A
The ratio of olefin, maleic acids and maleic imides is generally a molar ratio of α-olefin: (maleic acids + maleic imides) = 1:0.8~
1.2, preferably approximately 1:1, and maleic acids: maleic imides = 0.9 to 0.3: 0.1
The ratio is preferably 0.7, preferably 0.8 to 0.4:0.2 to 0.6. When the ratio of maleic acids is extremely small compared to α-olefin, it tends to be difficult to obtain a water-based adhesive, and the adhesive strength, especially the normal water-resistant adhesive strength and the heat-resistant adhesive strength, tend to decrease. When the ratio of maleic acids is extremely large compared to α-olefin, water-resistant adhesive strength and impact-resistant adhesive strength tend to decrease. When the amount of maleic acid imide is extremely large, it tends to be difficult to obtain a water-based adhesive. Although the degree of polymerization of copolymer A is not particularly limited, it is usually approximately 200 to 10,000. If the degree of polymerization is extremely lower than 200, workability such as coatability tends to decrease, and adhesive performance tends to decrease. Conversely, even when the degree of polymerization is extremely greater than 10,000, the same tendency as above occurs. In the present invention, the degree of polymerization of copolymer A is preferably within the range of 400 to 5,000. In the present invention, a partially or completely neutralized product of the copolymer A (hereinafter referred to as "component (a)") is used.
The degree of neutralization of copolymer A is generally 30 mol% or more based on the total number of carboxyl groups in the copolymer, preferably
It is preferable that it is neutralized by 40 mol% or more. The total number of carboxyl groups is the sum of carboxyl groups in the maleic acid moiety and one acid anhydride group in the maleic anhydride moiety converted into two carboxyl groups. Adhesive compositions obtained by blending component (a) with a neutralization degree of less than 30 mol% will crosslink within a short period of time, resulting in increased viscosity or gelation, which may slow down the coating process, or cause problems due to gelation. This is not preferable as it causes a decrease in wetting phenomenon and causes poor adhesion. Adhesive compositions obtained by blending component (a) with a low degree of neutralization generally have a relatively short pot life and a relatively fast curing rate. Furthermore, adhesive compositions obtained by blending component (a) with a high degree of neutralization generally have a relatively long pot life and a relatively slow curing rate. Therefore, the degree of neutralization of component (a) may be appropriately selected depending on the intended use of the adhesive composition so as to obtain the desired pot life and curing speed.
Component (a) is obtained by reacting copolymer A with a neutralizing agent. Such a neutralizing agent is not particularly limited, and a wide range of known basic compounds can be used, including ammonia (ammonia water), ammonia carbonate, phosphate or acetate, monoethanolamine, diethanolamine. , triethanolamine, other alkylolamines,
Organic amines such as aliphatic amines and aromatic amines,
Examples include oxides, hydroxides, or carbonates of alkaline earth metals, and weak acid salts such as hydroxides, carbonates, silicates, phosphates, and acetates of alkali metals. Among these are ammonia, carbonates of ammonia,
More preferred are organic amines and alkaline earth metal oxides, hydroxides, or carbonates. The amount of neutralizing agent used is not particularly limited, but if the degree of neutralization is 30
It is preferable to use an amount such that the amount is mol % or more and the pH of the adhesive composition obtained by blending component (a) is within the range of 4 to 10. When the pH value is less than 4, crosslinking is promoted by the acid component, and the coating process tends to deteriorate due to thickening or gelation, and the adhesiveness tends to decrease. Furthermore, when the pH exceeds 10, room temperature curability tends to be poor. The adhesive composition obtained by blending the component (a) has excellent room temperature curability, and even in the low temperature period of winter (5 to 10°C), it can be quickly cured by pressing for a shorter time. Excellent normal adhesive strength even after short-term curing,
Water resistant adhesive strength, heat resistant adhesive strength, boiling resistant repeated adhesive strength,
It exhibits high performance such as durable adhesive strength and impact resistant adhesive strength. Most preferably, maleic imide is introduced as the maleic imide. Compounds having two or more aziridine rings in the molecule (hereinafter referred to as "component (b)") used in the present invention include
【式】〔Ｒ及び
R′は同一又は相異なつて水素原子またはCnH2o+1
（ｎは１〜３の整数）を示す〕を２個以上有する
ものを広く使用できる。基[Formula] [R and R' are the same or different and hydrogen atoms or CnH 2o+1
(n is an integer of 1 to 3)] can be widely used. base
【式】または 基[expression] or base
【式】であるものが好ましく、斯か
る基が分子内に３個以上有するものがより好まし
い。(b)成分としては具体的には２，４，６−（ト
リエチレンイミノ）−sym−トリアジン（以下
「TEM」と略記）、ω−アジリジニルプロピオン
酸−２，２−ジヒドロキシメチル−ブタノール−
トリエステル（以下「TAZ」と略記）、２，４，
６−トリス（２−メチル−１−アジリジル）−
sym−トリアジン、２，４，６−トリス（２−エ
チル−１−アジリジル）−sym−トリアジン、ジ
フエニルメタン−bis−４，4′−Ｎ，N′−ジエチ
レンユリア〔即ち４，4′−ビス（エチレンイミノ
カルボニルアミノ）ジフエニルメタン〕（以下
「MDEI」と略記）、ビス（２−エチル−１−アジ
リジル）ベンゼン−１，３−ジカルボン酸アミ
ド、トリス（２−エチル−１−アジリジル）ベン
ゼン−１，３，５−トリカルボン酸アミド、ビス
（２−エチル−１−アジリジル）セバシン酸アミ
ド、１，６−ヘキサメチレンジエチレンユリア
〔即ち１，６−ビス（エチレンイミノカルボニル
アミノ）ヘキサン〕（以下「HDU」と略記）、
２，４−ジエチレンウレイドトルエン（以下
「TDEI」と略記）、１，1′−カルボニル−bis−エ
チレンイミン、ポリメチレン（C2〜C4）−bis−
エチレンユリア、Ｎ，N′−bis（４，６−ジエチ
レンイミノ−１，３，５−トリアジン−２−イ
ル）−ヘキサメチレンジアミノ等を例示できる。
これらのうちでTEM，TAZ，MDEI，HDU及び
TDEIが特に好ましい。(a)成分と(b)成分との配合
割合は一般に前者100重量部（以下単に「部」と
記す）に対して後者0.2〜200部である。200部よ
り極端に多くなると耐水、耐熱等の接着力が低下
する傾向となり、0.2部より極端に少なくなると
耐熱、耐水、耐煮沸繰返し等の接着力が低下して
くる傾向となる。(a)成分100部に対して後者を１
〜100部配合した時には本発明の所期の効果をよ
り一層発揮し得る。
本発明に於ては上記(a)成分及び(b)成分に水性ラ
テツクスを配合するのが好ましい。水性ラテツク
スを配合することにより耐衝撃接着力、耐水接着
力等の諸性能、塗工性等の作業性等をより一層向
上し得る。使用される水性ラテツクスとしては公
知のものを広く使用でき、具体的にはスチレン、
ブタジエン、アクリロニトリル、クロロプレン、
イソプレン、酢酸ビニル、エチレン、アクリル酸
エステル等から選ばれた１種または共重合可能な
２種以上の不飽和単量体からなる共重合体の分散
液や天然ゴムラテツクス等を例示できる。これら
のうちポリ酢酸ビニル水分散液及びスチレン−ブ
タジエン水分散液が好ましい。斯かる水性ラテツ
クスにはカルボキシル基、エポキシ基、ヒドロキ
シル基等の官能基を共重合等の手段により導入す
ることができる。カルボキシル基を導入した所謂
カルボキシル化変性ラテツクスがより好ましい。
水性ラテツクスの配合量としては、水性ラテツク
スを配合して得られる接着剤組成物のPHが４〜10
の範囲に止まるような量であればよく、一般に(a)
成分100部に対して水性ラテツクスの固形分換算
で10〜10000部である。(a)成分100部に対して水性
ラテツクスを固形分換算で50〜2000部配合した時
には上記効果をさらに一層発揮し得る。
また本発明に於ては上記(a)成分及び(b)成分に充
填剤を配合するのが好ましい。充填剤を配合する
ことにより耐熱接着力等の諸性能、塗工性等の作
業性等をより一層向上し得る。使用される充填剤
としてはこの分野で慣用のものを広く使用でき、
具体的には炭酸カルシウム、珪酸カルシウム、ア
ルミニウムシリケート、亜鉛華、炭酸亜鉛、クレ
ー、タルク、珪砂等の無機系充填剤、木粉、小麦
粉、大豆グルー等の有機系充填剤等を例示でき
る。これらのうち炭酸カルシウム、珪酸カルシウ
ム及び炭酸亜鉛が最も好ましい。斯かる充填剤の
配合量としては、充填剤を配合して得られる接着
剤組成物のPHが４〜10の範囲に止まるような量で
よく、一般に(a)成分100部に対して５〜2000部用
いられる。(a)成分100部に対して充填剤を50〜
1000部配合した時には上記効果をさらに一層発揮
し得る。
本発明では(a)成分及び(b)成分に水性ラテツクス
及び充填剤を配合するのが最も好ましい。
本発明に於ては使用目的に応じその他の第三成
分としてｎ−ブチルカルビトール等の可塑性高沸
点溶剤、フタル酸エステル等の可塑剤、界面活性
剤等を適宜配合することができる。
本発明組成物を製造するに際しては特に限定が
なくこの分野で慣用の手段を広く適用し得る。例
えば(a)成分の水溶液または水分散液に水性ラテツ
クス、充填剤、(b)成分その他第三成分を適宜添
加、混合することにより本発明組成物が製造され
る。添加及び混合は室温付近で行なうのがよく、
また(b)成分が液状、粉末状を問わずそのままで或
いは適当な有機溶媒又は水に溶解又は分散させた
形態で添加するのがよい。更に(b)成分はできるだ
け最後に添加混合するのが好ましく、接着剤組成
物の使用直前に(b)成分を配合するのが最も好まし
い。本発明組成物は(a)成分の代りに共重合体と中
和剤とを所定量混合したものを用い、該混合物に
(b)成分、水性ラテツクス、充填剤等を適宜添加す
ることによつても製造される。
本発明組成物の使用に際しては、該組成物を接
着が必要な箇所に塗付して圧締、養生すればよ
い。塗付方法としては特に限定されず公知の方法
を広く使用でき、例えば手刷毛による方法、ハン
ドローラーによる方法、自動スプレツダーによる
方法等を挙げることができる。使用される接着剤
組成物の固形分濃度は一般に10〜80重量％、好ま
しくは20〜70％にあるのがよい。塗付量としては
被着体の形状、寸法等により異なり一概には言え
ないが、180〜300ｇ／m2の範囲内が適当である。
圧締圧力及び圧締時間としては被着体の形状、寸
法等により異なり一概には言えないが、圧締圧力
は一般に５〜10Kg／cm2、圧締時間は夏期10分以
上、冬期20分以上とするのがよい。またプレス徐
圧後出荷迄に要する養生時間としては特に限定さ
れないが、夏期は１時間以上、冬期は２時間以上
とするのがよい。
本発明をより一層明らかにするために実施例を
以下に掲げる。
実施例 １
水270ｇ及びイソブチレン−無水マレイン酸−
マレイン酸イミド共重合体（共重合モル比0.5：
0.3：0.2、平均重合度400、粉末）150ｇの混合物
に、ほぼ完全中和状態になるように25％アンモニ
ア水80ｇを加え、加熱溶解させて溶液を得る。こ
の溶液450ｇにカルボキシル変性スチレン−ブタ
ジエン共重合体ラテツクス（共重合モル比0.6：
0.4、樹脂分当り５モル％のカルボキシル基導入
による変性、固形分48％、PH6.4）1000ｇ及び重
質炭酸カルシウム550ｇを添加し、混合物（PH
8.4、CR試験紙）を得る。この混合物を接着剤ベ
ースＢと称する。
接着剤ベースB100部にTEMの25％水溶液を２
部（TEM分として0.5部）配合して本発明組成物
Ｂ−１を得る。同様にTEMの25％水溶液を４部
（TEM分として１部）配合して本発明組成物Ｂ−
２を得る。尚比較のために接着剤ベースB100部
にそれぞれグリセリンジグリシジルエーテル（エ
ポキシ化合物）を１部、グリセリンジグリシジル
エーテルを５部、MDI系イソシアネート（商標ミ
リオネートMR，NCO含量30％、日本ポリウレタ
ン工業KK製）１部、MDI系イソシアネート
（同）５部、ポリエチレンイミン（平均分子量
400）５部を配合して、接着剤組成物Ｂ−３，Ｂ
−４，Ｂ−５，Ｂ−６及びＢ−７を得る。上記組
成物Ｂ−１乃至Ｂ−６のPHは8.4（CR試験紙）で
ある。またＢ−７のPHは9.8（TB試験紙）であ
る。
これら組成物を使用して再合板を作成した。即
ち被着材は6m／ｍのJASI類１等（舟艇用合板）
を30cm×30cm（以下尺角と略す）の正方形に切断
し同一繊維方向に貼合せて室温又は加熱接着し
た。室温接着及び加熱接着の貼合せ条件は以下の
通りである。
室温接着の貼合せ条件
塗布量：20ｇ／尺角
圧締圧：10Kg／cm2
圧締時間：２時間
圧締雰囲気：26〜28℃
加熱接着の貼合せ条件
塗布量：20ｇ／尺角
推積時間：10Kg×10分（25〜28℃）
圧締温度：130℃
圧締時間：８分
圧締圧：10Kg／cm2
室温接着又は加熱接着の後20℃、湿度60％の恒
温室にて、３日間養生し接着試験を行なつた。再
合板の接着試験は接着物を2.5cm（巾）×９cm（繊
維方向）の試験片に切断し、その中央部に接着面
の長さが1.5cmとなるように両面よりそれぞれ正
しく接着面に達する鋸目を入れ2.5cm×1.5cmの接
着面積となした試験片について引張せん断強度の
測定を行なつた。常態接着強度は、接着物を未処
理のまま供試したものである。耐水接着強度は、
接着物を20℃の水中に24時間浸漬後濡れたままの
状態で直ちに供試したものである。耐温水接着強
度は60℃の温水中に３時間浸漬後20℃の水中に20
分浸漬して濡れれたままの状態で直ちに供試した
ものである。また煮沸繰返し接着強度は沸騰水中
に４時間浸漬後60℃オーブン中で16時間乾燥、次
いで沸騰水中に４時間浸漬後20℃の水中に20分浸
漬して濡れたままの状態で直ちに供試したもので
ある。得られた結果を下記第１表に示す。[Formula] is preferable, and those having three or more such groups in the molecule are more preferable. Specifically, the component (b) is 2,4,6-(triethyleneimino)-sym-triazine (hereinafter abbreviated as "TEM"), ω-aziridinylpropionic acid-2,2-dihydroxymethyl-butanol. −
Triester (hereinafter abbreviated as "TAZ"), 2, 4,
6-tris(2-methyl-1-aziridyl)-
sym-triazine, 2,4,6-tris(2-ethyl-1-aziridyl)-sym-triazine, diphenylmethane-bis-4,4'-N,N'-diethylene urea [i.e. 4,4'-bis( ethyleneiminocarbonylamino) diphenylmethane] (hereinafter abbreviated as "MDEI"), bis(2-ethyl-1-aziridyl)benzene-1,3-dicarboxylic acid amide, tris(2-ethyl-1-aziridyl)benzene-1, 3,5-tricarboxylic acid amide, bis(2-ethyl-1-aziridyl) sebacic acid amide, 1,6-hexamethylene diethylene urea [i.e. 1,6-bis(ethyleneiminocarbonylamino)hexane] (hereinafter referred to as "HDU") ),
2,4-diethyleneureidotoluene (hereinafter abbreviated as "TDEI"), 1,1'-carbonyl-bis-ethyleneimine, polymethylene (C 2 - C 4 )-bis-
Examples include ethylene urea, N,N'-bis(4,6-diethyleneimino-1,3,5-triazin-2-yl)-hexamethylene diamino, and the like.
Among these, TEM, TAZ, MDEI, HDU and
TDEI is particularly preferred. The mixing ratio of components (a) and (b) is generally 100 parts by weight (hereinafter simply referred to as "parts") of the former and 0.2 to 200 parts by weight of the latter. When the amount is extremely greater than 200 parts, adhesive strength such as water resistance and heat resistance tends to decrease, and when it is extremely less than 0.2 part, adhesive strength such as heat resistance, water resistance, and repeated boiling resistance tends to decrease. (a) 1 part of the latter per 100 parts of ingredient
When blending 100 parts to 100 parts, the desired effect of the present invention can be further exhibited. In the present invention, it is preferable to mix an aqueous latex with the above components (a) and (b). By blending an aqueous latex, various performances such as impact-resistant adhesive strength and water-resistant adhesive strength, and workability such as coatability can be further improved. A wide range of known aqueous latexes can be used, specifically styrene,
butadiene, acrylonitrile, chloroprene,
Examples include dispersions of copolymers made of one or more copolymerizable unsaturated monomers selected from isoprene, vinyl acetate, ethylene, acrylic esters, etc., natural rubber latex, and the like. Among these, polyvinyl acetate aqueous dispersion and styrene-butadiene aqueous dispersion are preferred. Functional groups such as carboxyl groups, epoxy groups, and hydroxyl groups can be introduced into such aqueous latexes by means such as copolymerization. More preferred is a so-called carboxylated modified latex into which a carboxyl group has been introduced.
The amount of water-based latex blended is such that the pH of the adhesive composition obtained by blending the water-based latex is 4 to 10.
It suffices if the amount stays within the range of (a)
The solid content of the aqueous latex is 10 to 10,000 parts per 100 parts of the ingredients. When 50 to 2000 parts of aqueous latex is blended in terms of solid content with respect to 100 parts of component (a), the above effects can be exhibited even more. Further, in the present invention, it is preferable to mix a filler with the above-mentioned components (a) and (b). By blending fillers, various performances such as heat-resistant adhesive strength, workability such as coating properties, etc. can be further improved. A wide range of fillers commonly used in this field can be used.
Specific examples include inorganic fillers such as calcium carbonate, calcium silicate, aluminum silicate, zinc white, zinc carbonate, clay, talc, and silica sand, and organic fillers such as wood flour, wheat flour, and soybean glue. Among these, calcium carbonate, calcium silicate and zinc carbonate are most preferred. The amount of such filler to be blended may be such that the pH of the adhesive composition obtained by blending the filler remains within the range of 4 to 10, and generally 5 to 10 parts per 100 parts of component (a). 2000 copies used. (a) 50 to 50 parts of filler per 100 parts of component
When 1000 parts are mixed, the above effects can be exhibited even more. In the present invention, it is most preferable to mix an aqueous latex and a filler with components (a) and (b). In the present invention, other third components such as a plastic high-boiling solvent such as n-butylcarbitol, a plasticizer such as a phthalate ester, a surfactant, etc. may be appropriately blended according to the purpose of use. When producing the composition of the present invention, there are no particular limitations, and means commonly used in this field can be widely applied. For example, the composition of the present invention can be produced by appropriately adding and mixing an aqueous latex, filler, component (b), and other third components to an aqueous solution or dispersion of component (a). It is best to add and mix at room temperature.
In addition, component (b) is preferably added as it is, whether in liquid or powder form, or in a form dissolved or dispersed in an appropriate organic solvent or water. Further, it is preferable that component (b) is added and mixed as last as possible, and most preferably, component (b) is blended immediately before use of the adhesive composition. The composition of the present invention uses a mixture of a predetermined amount of a copolymer and a neutralizing agent instead of component (a), and
It can also be produced by appropriately adding component (b), an aqueous latex, a filler, etc. When using the composition of the present invention, the composition may be applied to the area where adhesion is required, pressed and cured. The application method is not particularly limited and a wide variety of known methods can be used, such as a method using a hand brush, a method using a hand roller, and a method using an automatic spreader. The solids concentration of the adhesive composition used is generally between 10 and 80% by weight, preferably between 20 and 70%. Although the coating amount varies depending on the shape and dimensions of the adherend and cannot be generalized, it is suitably within the range of 180 to 300 g/m 2 .
The clamping pressure and clamping time vary depending on the shape and dimensions of the adherend and cannot be generalized, but the clamping pressure is generally 5 to 10 kg/cm 2 , and the clamping time is 10 minutes or more in summer and 20 minutes in winter. It is better to set it to the above. The curing time required after press decompression before shipping is not particularly limited, but it is preferably 1 hour or more in summer and 2 hours or more in winter. Examples are given below to further clarify the present invention. Example 1 270 g of water and isobutylene-maleic anhydride
Maleic acid imide copolymer (copolymerization molar ratio 0.5:
0.3:0.2, average degree of polymerization 400, powder) 80 g of 25% ammonia water is added to a mixture of 150 g to almost completely neutralize the mixture, and the mixture is heated and dissolved to obtain a solution. Add carboxyl-modified styrene-butadiene copolymer latex (copolymerization molar ratio 0.6:
0.4, modified by introducing 5 mol% carboxyl group per resin content, solid content 48%, PH 6.4) and 550 g of heavy calcium carbonate were added, and the mixture (PH
8.4, get CR test paper). This mixture is referred to as Adhesive Base B. Add 25% aqueous solution of TEM to 100 parts of adhesive base B.
(0.5 part as TEM part) to obtain composition B-1 of the present invention. Similarly, 4 parts of a 25% aqueous solution of TEM (1 part as TEM content) was added to form composition B-
Get 2. For comparison, 100 parts of adhesive base B, 1 part of glycerin diglycidyl ether (epoxy compound), 5 parts of glycerin diglycidyl ether, MDI isocyanate (trademark Millionate MR, NCO content 30%, manufactured by Nippon Polyurethane Kogyo KK) ) 1 part MDI isocyanate (same), polyethyleneimine (average molecular weight
400) Adhesive composition B-3,B by blending 5 parts
-4, B-5, B-6 and B-7 are obtained. The pH of the compositions B-1 to B-6 is 8.4 (CR test paper). In addition, the pH of B-7 is 9.8 (TB test paper). Re-plywood was made using these compositions. In other words, the adherend material is 6m/m JASI class 1 (plywood for boats)
was cut into squares of 30 cm x 30 cm (hereinafter abbreviated as "shaku-ku"), laminated in the same fiber direction, and bonded at room temperature or by heating. The bonding conditions for room temperature adhesion and heat adhesion are as follows. Lamination conditions for room temperature adhesive Coating amount: 20g/square inch Clamping pressure: 10Kg/cm 2 Clamping time: 2 hours Pressing atmosphere: 26-28℃ Lamination conditions for heat adhesive Coating amount: 20g/square inch Estimated Time: 10Kg x 10 minutes (25-28℃) Pressing temperature: 130℃ Pressing time: 8 minutes Pressing pressure: 10Kg/cm 2 After room temperature bonding or heat bonding, in a constant temperature room at 20℃ and 60% humidity. After curing for 3 days, an adhesion test was conducted. For adhesion testing of re-plywood, cut the adhesive into test pieces of 2.5 cm (width) x 9 cm (fiber direction), and place a piece of paper on both sides so that the length of the adhesive surface is 1.5 cm in the center of the specimen. Tensile shear strength was measured on a test piece with a 2.5 cm x 1.5 cm bonding area made by making a serration. The normal adhesive strength is measured by testing the adhesive without any treatment. Water resistant adhesive strength is
The adhesive was immersed in water at 20°C for 24 hours and then immediately tested while still wet. Hot water resistant adhesive strength is 20°C in water at 20°C after immersion in hot water at 60°C for 3 hours.
It was immersed for a minute and then tested immediately while still wet. In addition, repeated boiling bond strength was tested by immersing in boiling water for 4 hours, drying in a 60℃ oven for 16 hours, then immersing in boiling water for 4 hours, then immersing in 20℃ water for 20 minutes, and then testing immediately while still wet. It is something. The results obtained are shown in Table 1 below.
【表】
実施例 ２
イソブチレン−無水マレイン酸（共重合比
0.5：0.5、平均重合度400、粉末）アンモニア雰
囲気下60℃で反応させた後更に180℃に加熱して
イソブチレン−無水マレイン酸−マレイン酸イミ
ド共重合体（共重合比0.5：0.3：0.2）を得る。こ
の共重合体150ｇと水285ｇとからなる水分散液に
25％アンモニア水65ｇを加え90℃以上で４時間攪
拌溶解して溶液を得る。この溶液200ｇにカルボ
キシル変性スチレン−ブタジエン共重合体ラテツ
クス（共重合比モル比0.6：0.4、モノマー当り５
モル％のカルボキシル基導入、固形分48％、PH
6.4〔BTB〕）500ｇと重質炭酸カルシウム300ｇを
加えた混合物を接着剤ベースとした。
該接着ベース100ｇに25％TEM水溶液２ｇ
（TEM分0.5ｇ）を加え接着剤を得た。これを番
号３−１で表わす。尚比較の為に、上記接着剤ベ
ース100ｇにグリセリンジグリシジルエーテル３
ｇを配合して接着剤（番号：３−２）を得た。ま
た上記接着剤ベースに何も配合しないものを接着
剤（番号：３−３）として使用した。これら３種
の接着剤のPHはすべて8.2（CR試験紙）であつ
た。
更にイソブチレン−無水マレイン酸（共重合比
0.5：0.5、平均重合度400、粉末）をイミド化し
ない以外は、上記と同様にして接着剤ベースを
得、この接着剤ベース100ｇに25％TEM水溶液２
ｇ（TEM分0.5ｇ）を加えて接着剤（番号：３−
４）を得た。
これら接着剤を使用して下記貼合せ条件で硬く
木破を生じ難い広葉樹種であるカバ材（マサ目、
厚さ10m／ｍ、幅25m／ｍ）相互を同一繊維方向
に貼合せた。
貼合せ条件
塗付量：200ｇ／m2
圧締圧力：10Kg／cm2
圧締時間：24時間
圧締温度：20℃
養生日数：２日又は７日
養生温度：20〜22℃
JIS Ｋ−6852に準じて試験片を作成し、圧縮せ
ん断接着力試験を行なつた。尚耐熱試験は60℃恒
温乾燥器に24時間放置後直ちに供試し、常態、耐
水、耐温水及び煮沸繰返し試験は実施例１と同様
に行なつた（試験時雰囲気：温度20℃、湿度60％
PH、被着体の含有率：９〜10％）。得られた結果
を下記第２表に示す。[Table] Example 2 Isobutylene-maleic anhydride (copolymerization ratio
0.5:0.5, average degree of polymerization 400, powder) React at 60°C in an ammonia atmosphere and then further heat to 180°C to produce isobutylene-maleic anhydride-maleic acid imide copolymer (copolymerization ratio 0.5:0.3:0.2) get. An aqueous dispersion consisting of 150g of this copolymer and 285g of water
Add 65 g of 25% ammonia water and stir and dissolve at 90°C or higher for 4 hours to obtain a solution. Add 200 g of this solution to carboxyl-modified styrene-butadiene copolymer latex (copolymerization molar ratio 0.6:0.4, 5% per monomer).
Mol% carboxyl group introduction, solid content 48%, PH
The adhesive base was a mixture of 500 g of 6.4 [BTB] and 300 g of heavy calcium carbonate. 2g of 25% TEM aqueous solution to 100g of the adhesive base
(TEM content: 0.5 g) was added to obtain an adhesive. This is represented by number 3-1. For comparison, add glycerin diglycidyl ether 3 to 100g of the above adhesive base.
g was blended to obtain an adhesive (number: 3-2). Further, an adhesive (number: 3-3) in which nothing was added to the above adhesive base was used. The pH of all three adhesives was 8.2 (CR test paper). Furthermore, isobutylene-maleic anhydride (copolymerization ratio
0.5:0.5, average degree of polymerization 400, powder) was obtained in the same manner as above except that the powder was not imidized, and 25% TEM aqueous solution 2 was added to 100 g of this adhesive base.
g (0.5 g for TEM) and adhesive (number: 3-
4) was obtained. Using these adhesives, the following bonding conditions are used: birch wood, which is a hard hardwood species that does not easily break,
(thickness: 10 m/m, width: 25 m/m) were laminated together in the same fiber direction. Lamination conditions Coating amount: 200g/m 2 Clamping pressure: 10 Kg/cm 2 Clamping time: 24 hours Clamping temperature: 20℃ Curing days: 2 or 7 days Curing temperature: 20 to 22℃ JIS K-6852 Test specimens were prepared according to the method described in 2007, and a compression shear adhesion test was conducted. The heat resistance test was carried out immediately after being left in a constant temperature dryer at 60°C for 24 hours, and the normal state, water resistance, hot water resistance, and repeated boiling tests were conducted in the same manner as in Example 1 (atmosphere during testing: temperature 20°C, humidity 60%).
PH, adherend content: 9-10%). The results obtained are shown in Table 2 below.
【表】
第２表から接着剤ベース３−３にグリセリンジ
グリシジルエーテルを添加しても各強度は若干向
上するだけであるが、該接着剤ベースにTEMを
添加した時には各強度は著しく向上することがわ
かる。
実施例 ３
実施例２と同じ接着剤を用い低温における接着
発現性をみるため環境試験室を用い、下記貼合せ
条件で接着させる以外は実施例２と同様にしてカ
バ材相互の圧縮せん断接着力の測定を行なつた。
得られた結果を下記第３表に示す。
貼合せ条件
塗付量：200ｇ／m2
圧締圧力：10Kg／cm2
圧締時間：24時間
圧締温度：８℃、湿度40％
養生温度：８〜10℃、湿度40〜45％RH
養生日数：２日、７日又は14日[Table] From Table 2, adding glycerin diglycidyl ether to adhesive base 3-3 only slightly improves each strength, but when TEM is added to the adhesive base, each strength improves markedly. I understand that. Example 3 The same adhesive as in Example 2 was used, an environmental test chamber was used to check the adhesion development at low temperatures, and the compressive shear adhesive strength between the cover materials was measured in the same manner as in Example 2, except that the bonding was performed under the following bonding conditions. Measurements were made.
The results obtained are shown in Table 3 below. Lamination conditions Coating amount: 200g/m 2 Clamping pressure: 10 Kg/cm 2 Clamping time: 24 hours Clamping temperature: 8℃, Humidity 40% Curing temperature: 8-10℃, Humidity 40-45%RH Curing Number of days: 2 days, 7 days or 14 days
【表】【table】
【表】
第３表から本発明の接着剤は低温貼合せに於け
る各強度に優れ低温硬化性の点で従来の接着剤に
比し著しく優つていることがわかる。
実施例 ４
実施例２と同様にしてイソブチレン−無水マレ
イン酸−マレイン酸イミド（共重合モル比0.5：
0.3：0.2、平均重合度600、粉末）150ｇ、25％ア
ンモニア水40ｇ及び310ｇからなる溶液を得た。
この溶液200ｇ、完全ケン化ポリビニルアルコー
ルを保護コロイドとして通常の乳化重合で調整し
たポリ酢酸ビニルエマルジヨン（PVA含量：酢
酸ビニルモノマー当り12％、固形分45％、PH4.4
〔BCG〕）400ｇ及び重質炭酸カルシウム180ｇを
攪拌混合して接着ベースを得た。
該接着剤ベース100ｇ当り25％MDEI水分散液
2.5ｇ（MDEI分0.65ｇ）及び５ｇ（MDEI分1.25
ｇ）を配合してそれぞれ接着剤５−１，５−２を
得た。これら接着剤のPHは共に6.8（BTB試験
紙）であつた。尚比較の為に上記接着剤ベース
100ｇにグリセリンジグリシジルエーテル５ｇを
配合して接着剤５−３を得た。また上記接着剤ベ
ースに何も配合しないものを接着剤５−４として
使用した。また特開昭49−93451号に基づいて得
られた市販アルカリ性α−オレフイン系接着剤
（商標ボンドタツクSH2、粘度20000cps、固形分
50％、PH13〔ALB試験紙〕、コニシKK製）100ｇ
当りグリセリンジグリシジルエーテル５ｇを配合
して接着剤５−５を得た。接着剤５−３及び５−
４のPHはすべて6.8（BTB試験紙）であつた。
更にイソブチレン−無水マレイン酸（共重合比
0.5：0.5、平均重合度600、粉末）をイミド化し
ない以外は、上記と同様にして接着剤ベースを
得、この接着剤ベース100ｇに25％MDEI水溶液
2.5ｇ（MDEI分0.625ｇ）及び５ｇ（MDEI分1.25
ｇ）を加えて、それぞれ接着剤（番号：５−
６）、接着剤（番号：５−７）を得た。
上記各種接着剤の初期接着発現性を調べるため
に20℃で圧締時間を10分、20分又は40分とする以
外は実施例２と同様にして常態強度を求めた。得
られた結果を下記第４表に示す。また実施例２と
同じ条件下で24時間圧締し、７日間養生して得ら
れる被着材の接着性能を実施例２と同様にして試
験した。この結果を第５表に併せて示す。Table 3 shows that the adhesive of the present invention has excellent strength in low temperature lamination and is significantly superior to conventional adhesives in terms of low temperature curability. Example 4 Isobutylene-maleic anhydride-maleic acid imide (copolymerization molar ratio 0.5:
A solution consisting of 0.3:0.2, average degree of polymerization 600, 150 g of powder), 40 g of 25% aqueous ammonia, and 310 g was obtained.
200g of this solution, polyvinyl acetate emulsion prepared by normal emulsion polymerization using fully saponified polyvinyl alcohol as a protective colloid (PVA content: 12% based on vinyl acetate monomer, solid content 45%, PH 4.4)
[BCG]) and 180 g of heavy calcium carbonate were stirred and mixed to obtain an adhesive base. 25% MDEI water dispersion per 100g of adhesive base
2.5g (MDEI 0.65g) and 5g (MDEI 1.25)
g) to obtain adhesives 5-1 and 5-2, respectively. The pH of both these adhesives was 6.8 (BTB test paper). For comparison, the above adhesive base
Adhesive 5-3 was obtained by blending 5 g of glycerin diglycidyl ether with 100 g. Also, the adhesive base without any addition was used as adhesive 5-4. In addition, a commercially available alkaline α-olefin adhesive (trademark BOND TACK SH2, viscosity 20000 cps, solid content
50%, PH13 [ALB test paper], manufactured by Konishi KK) 100g
Adhesive 5-5 was obtained by blending 5 g of glycerin diglycidyl ether per adhesive. Adhesive 5-3 and 5-
The pH of all 4 samples was 6.8 (BTB test paper). Furthermore, isobutylene-maleic anhydride (copolymerization ratio
Obtain an adhesive base in the same manner as above, except that the powder (0.5:0.5, average degree of polymerization 600, powder) is not imidized, and add 25% MDEI aqueous solution to 100 g of this adhesive base.
2.5g (MDEI 0.625g) and 5g (MDEI 1.25g)
g) and adhesive (number: 5-
6), an adhesive (number: 5-7) was obtained. In order to investigate the initial adhesion development properties of the above various adhesives, the normal strength was determined in the same manner as in Example 2, except that the pressing time was changed to 10 minutes, 20 minutes or 40 minutes at 20°C. The results obtained are shown in Table 4 below. Furthermore, the adhesive performance of the adherend obtained by pressing for 24 hours under the same conditions as in Example 2 and curing for 7 days was tested in the same manner as in Example 2. The results are also shown in Table 5.
【表】
上記第４表の初期接着発現性に於て、本発明接
着剤は従来の接着剤のうち最も優れているとされ
ていた接着剤５−５に比し、より一段と優れてい
ることがわかる。また養生７日目の接着性能につ
いても本発明接着剤は従来の接着剤に比し著しく
優つている。
実施例 ５
実施例４と同一の接着剤及びカバ材を使用し、
JIS Ｋ−6855に準じて耐衝撃性試験を行なつた。
貼合せ条件は実施例２に準じた。得られた結果を
下記第５表に示す。[Table] In terms of initial adhesion development properties shown in Table 4 above, the adhesive of the present invention is much better than Adhesive 5-5, which was considered to be the best among conventional adhesives. I understand. Furthermore, the adhesive of the present invention is significantly superior to conventional adhesives in terms of adhesive performance on the 7th day of curing. Example 5 Using the same adhesive and cover material as Example 4,
An impact resistance test was conducted according to JIS K-6855.
The bonding conditions were the same as in Example 2. The results obtained are shown in Table 5 below.
【表】【table】
Claims (1)
イン酸イミド類の共重合体の部分もしくは完全
中和物、及び (b) 分子内に２個以上のアジリジン環を有する化
合物 を含有せしめてなる水性接着剤組成物。 ２ 共重合体の中和物の中和度が30モル％以上で
ある特許請求の範囲第１項に記載の接着剤組成
物。 ３ α−オレフインがイソブチレンである特許請
求の範囲第１項又は第２項に記載の接着剤組成
物。 ４ マレイン酸イミド類がマレイン酸イミドであ
る特許請求の範囲第１項乃至第３項のいずれかに
記載の接着剤組成物。 ５ (b)成分が２，４，６−（トリエチレンイミ
ノ）−sym−トリアジン、ω−アジリジニルプロ
ピオン酸−２，２−ジヒドロキシメチル−ブタノ
ール−トリエステル、２，４，６−トリス（２−
メチル−１−アジリジル）−sym−トリアジン、
２，４，６−トリス（２−エチル−１−アジリジ
ル）−sym−トリアジン、ジフエニルメタン−bis
−４，4′−Ｎ，N′−ジエチルユリア、１，６−ヘ
キサメチレンジエチレンユリア、ビス（２−エチ
ル−１−アジリジル）ベンゼン−１，３−ジカル
ボン酸アミド、トリス（２−エチル−１−アジリ
ジル）ベンゼン−１，３−５−トリカルボン酸ア
ミド、ビス（２−エチル−１−アジリジル）セバ
シン酸アミド、２，４−ジエチレンウレイドトル
エン、１，1′−カルボニル−bis−エチレンイミ
ン、ポリメチレン（C2〜C4）−bis−エチレンユ
リア及びＮ，N′−bis（４，６−ジエチレンイミ
ノ−１，３，５−トリアジン−２−イル）−ヘキ
サメチレンジアミンから選ばれた少なくとも１種
である特許請求の範囲第１項乃至第４項のいずれ
かに記載の接着剤組成物。 ６ (a)成分と(b)成分との配合割合が前者100重量
部に対して後者が0.2〜200重量部である特許請求
の範囲第１項乃至第５項のいずれかに記載の接着
剤組成物。 ７ 水性ラテツクスを配合した特許請求の範囲第
１項乃至第６項のいずれかに記載の接着剤組成
物。 ８ 水性ラテツクスがポリ酢酸ビニル水分散液及
びカルボキシル化変性されたスチレン−ブタジエ
ン水分散液から選ばれた少なくとも１種である特
許請求の範囲第１項乃至第７項のいずれかに記載
の接着剤組成物。 ９ 充填剤を配合した特許請求の範囲第１項乃至
第８項のいずれかに記載の接着剤組成物。 １０ 充填剤が炭酸カルシウム、珪酸カルシウム
及び炭酸亜鉛から選ばれた少なくとも１種である
特許請求の範囲第１項乃至第９項のいずれかに記
載の接着剤組成物。 １１ PHが４〜10の範囲にある特許請求の範囲第
１項乃至第１０項のいずれかに記載の接着剤組成
物。[Scope of Claims] 1. (a) partially or completely neutralized copolymers of α-olefin, maleic acids and maleic imides, and (b) compounds having two or more aziridine rings in the molecule. An aqueous adhesive composition comprising: 2. The adhesive composition according to claim 1, wherein the degree of neutralization of the neutralized copolymer is 30 mol% or more. 3. The adhesive composition according to claim 1 or 2, wherein the α-olefin is isobutylene. 4. The adhesive composition according to any one of claims 1 to 3, wherein the maleic acid imide is maleic acid imide. 5 Component (b) is 2,4,6-(triethyleneimino)-sym-triazine, ω-aziridinylpropionic acid-2,2-dihydroxymethyl-butanol-triester, 2,4,6-tris( 2-
methyl-1-aziridyl)-sym-triazine,
2,4,6-tris(2-ethyl-1-aziridyl)-sym-triazine, diphenylmethane-bis
-4,4'-N,N'-diethyl urea, 1,6-hexamethylene diethylene urea, bis(2-ethyl-1-aziridyl)benzene-1,3-dicarboxylic acid amide, tris(2-ethyl-1 -aziridyl)benzene-1,3-5-tricarboxylic acid amide, bis(2-ethyl-1-aziridyl)sebacic acid amide, 2,4-diethyleneureidotoluene, 1,1'-carbonyl-bis-ethyleneimine, polymethylene At least one member selected from ( C2 - C4 )-bis-ethylene urea and N,N'-bis(4,6-diethyleneimino-1,3,5-triazin-2-yl)-hexamethylenediamine An adhesive composition according to any one of claims 1 to 4. 6. The adhesive according to any one of claims 1 to 5, wherein the blending ratio of component (a) and component (b) is 100 parts by weight of the former and 0.2 to 200 parts by weight of the latter. Composition. 7. The adhesive composition according to any one of claims 1 to 6, which contains an aqueous latex. 8. The adhesive according to any one of claims 1 to 7, wherein the aqueous latex is at least one selected from an aqueous polyvinyl acetate dispersion and an aqueous carboxylation-modified styrene-butadiene dispersion. Composition. 9. The adhesive composition according to any one of claims 1 to 8, which contains a filler. 10. The adhesive composition according to any one of claims 1 to 9, wherein the filler is at least one selected from calcium carbonate, calcium silicate, and zinc carbonate. 11. The adhesive composition according to any one of claims 1 to 10, having a PH in the range of 4 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10910477A JPS5441940A (en) | 1977-09-09 | 1977-09-09 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10910477A JPS5441940A (en) | 1977-09-09 | 1977-09-09 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5441940A JPS5441940A (en) | 1979-04-03 |
| JPS624431B2 true JPS624431B2 (en) | 1987-01-30 |
Family
ID=14501670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10910477A Granted JPS5441940A (en) | 1977-09-09 | 1977-09-09 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5441940A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1261614A (en) * | 1984-04-27 | 1989-09-26 | Shmuel Dabi | Crosslinked carboxyl polyelectrolytes and method of making same |
| JPS60180515U (en) * | 1984-05-11 | 1985-11-30 | ワイケイケイ株式会社 | Slider pulling device |
| JPH0527046Y2 (en) * | 1986-04-15 | 1993-07-09 | ||
| JPH0719289Y2 (en) * | 1987-08-07 | 1995-05-10 | ワイケイケイ株式会社 | Lifting device for slide fastener slider |
| US5300602A (en) * | 1992-03-30 | 1994-04-05 | Nippon Shokubai Co., Ltd. | Process for producing water-soluble polymer and water-soluble polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137930A (en) * | 1974-09-27 | 1976-03-30 | Cemedine Co Ltd | SETSUCHAKUSEISOSEIBUTSU |
-
1977
- 1977-09-09 JP JP10910477A patent/JPS5441940A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137930A (en) * | 1974-09-27 | 1976-03-30 | Cemedine Co Ltd | SETSUCHAKUSEISOSEIBUTSU |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5441940A (en) | 1979-04-03 |
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