IE83707B1 - Activator compositions for cyanoacrylate adhesives - Google Patents
Activator compositions for cyanoacrylate adhesivesInfo
- Publication number
- IE83707B1 IE83707B1 IE2000/0367A IE20000367A IE83707B1 IE 83707 B1 IE83707 B1 IE 83707B1 IE 2000/0367 A IE2000/0367 A IE 2000/0367A IE 20000367 A IE20000367 A IE 20000367A IE 83707 B1 IE83707 B1 IE 83707B1
- Authority
- IE
- Ireland
- Prior art keywords
- activator
- composition according
- group
- optionally substituted
- adhesive
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 144
- 239000012190 activator Substances 0.000 title claims description 139
- 239000004830 Super Glue Substances 0.000 title claims description 46
- 239000000853 adhesive Substances 0.000 claims description 67
- 230000001070 adhesive Effects 0.000 claims description 67
- 239000000758 substrate Substances 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 31
- 150000002894 organic compounds Chemical class 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 22
- -1 alkyl 3,5-pyridine dicarboxylates Chemical class 0.000 claims description 19
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 19
- GYVGXEWAOAAJEU-UHFFFAOYSA-N N,N,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000005842 heteroatoms Chemical group 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 10
- 230000000875 corresponding Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Nicotinic acid Natural products OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 6
- WPGHPGAUFIJVJF-UHFFFAOYSA-N 3,5-dichloropyridine Chemical compound ClC1=CN=CC(Cl)=C1 WPGHPGAUFIJVJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 150000003222 pyridines Chemical group 0.000 claims description 5
- 150000003248 quinolines Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- HAXFWIACAGNFHA-UHFFFAOYSA-N 2,2'-Dipyridyldisulfide Chemical compound C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 claims description 4
- SOSPMXMEOFGPIM-UHFFFAOYSA-N 3,5-dibromopyridine Chemical compound BrC1=CN=CC(Br)=C1 SOSPMXMEOFGPIM-UHFFFAOYSA-N 0.000 claims description 4
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims description 4
- HXEWMTXDBOQQKO-UHFFFAOYSA-N 4,7-dichloroquinoline Chemical compound ClC1=CC=NC2=CC(Cl)=CC=C21 HXEWMTXDBOQQKO-UHFFFAOYSA-N 0.000 claims description 4
- 229940111121 antirheumatic drugs Quinolines Drugs 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 235000001968 nicotinic acid Nutrition 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000003230 pyrimidines Chemical group 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 3
- NDDZXHOCOKCNBM-UHFFFAOYSA-N 5-nitroquinoline Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=N1 NDDZXHOCOKCNBM-UHFFFAOYSA-N 0.000 claims description 3
- GSASOFRDSIKDSN-UHFFFAOYSA-N 6-[(5-carboxypyridin-2-yl)disulfanyl]pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1SSC1=CC=C(C(O)=O)C=N1 GSASOFRDSIKDSN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001241 acetals Chemical class 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UACGDGTZNFKYQI-UHFFFAOYSA-N 4-tert-butyl-2-[(4-tert-butyl-1-propan-2-ylimidazol-2-yl)disulfanyl]-1-propan-2-ylimidazole Chemical compound CC(C)N1C=C(C(C)(C)C)N=C1SSC1=NC(C(C)(C)C)=CN1C(C)C UACGDGTZNFKYQI-UHFFFAOYSA-N 0.000 claims 1
- RBMXRAQYVULXPP-UHFFFAOYSA-N 4-tert-butyl-2-[(4-tert-butyl-5-propan-2-yl-1H-imidazol-2-yl)disulfanyl]-5-propan-2-yl-1H-imidazole Chemical compound CC(C)(C)C1=C(C(C)C)NC(SSC=2NC(=C(N=2)C(C)(C)C)C(C)C)=N1 RBMXRAQYVULXPP-UHFFFAOYSA-N 0.000 claims 1
- 150000003216 pyrazines Chemical group 0.000 claims 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 1
- DFPOZTRSOAQFIK-UHFFFAOYSA-N Dimethylsulfoniopropionate Chemical compound C[S+](C)CCC([O-])=O DFPOZTRSOAQFIK-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000011111 cardboard Substances 0.000 description 16
- 230000004913 activation Effects 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 210000003491 Skin Anatomy 0.000 description 10
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 9
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical class OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- FGBJXOREULPLGL-UHFFFAOYSA-N Ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 6
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- GYCPLYCTMDTEPU-UHFFFAOYSA-N 5-bromopyrimidine Chemical compound BrC1=CN=CN=C1 GYCPLYCTMDTEPU-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229960001701 Chloroform Drugs 0.000 description 2
- 241000710177 Citrus tristeza virus Species 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N Dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 230000000269 nucleophilic Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 230000003014 reinforcing Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- CRPTXKKKIGGDBX-UHFFFAOYSA-N (Z)-but-2-ene Chemical group [CH2]C=CC CRPTXKKKIGGDBX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-Heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- YZNQITSGDRCUKE-UHFFFAOYSA-N 1-chloropropane Chemical group [CH2]CCCl YZNQITSGDRCUKE-UHFFFAOYSA-N 0.000 description 1
- OBSLLHNATPQFMJ-UHFFFAOYSA-N 2,4-Dimethylthiazole Chemical compound CC1=CSC(C)=N1 OBSLLHNATPQFMJ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-Methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- UDAIGHZFMLGNDQ-UHFFFAOYSA-N 2-nitroquinoline Chemical class C1=CC=CC2=NC([N+](=O)[O-])=CC=C21 UDAIGHZFMLGNDQ-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N 3-aminopropanol Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- MXDRPNGTQDRKQM-UHFFFAOYSA-N 3-methylpyridazine Chemical compound CC1=CC=CN=N1 MXDRPNGTQDRKQM-UHFFFAOYSA-N 0.000 description 1
- ZUGAIMFLQLPTKB-UHFFFAOYSA-N 3-pyridin-3-ylpropan-1-ol Chemical compound OCCCC1=CC=CN=C1 ZUGAIMFLQLPTKB-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-Bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- UHBAPGWWRFVTFS-UHFFFAOYSA-N 4,4'-dipyridyl disulfide Chemical compound C=1C=NC=CC=1SSC1=CC=NC=C1 UHBAPGWWRFVTFS-UHFFFAOYSA-N 0.000 description 1
- XDADSGBUZWZQQQ-UHFFFAOYSA-N 4-bromopyrimidine Chemical compound BrC1=CC=NC=N1 XDADSGBUZWZQQQ-UHFFFAOYSA-N 0.000 description 1
- FEXIEMAAKBNTFK-UHFFFAOYSA-N 4-nitropyridine Chemical compound [O-][N+](=O)C1=CC=NC=C1 FEXIEMAAKBNTFK-UHFFFAOYSA-N 0.000 description 1
- FQIUCPGDKPXSLL-UHFFFAOYSA-N 5-bromopyridine-3-carboxylic acid Chemical compound OC(=O)C1=CN=CC(Br)=C1 FQIUCPGDKPXSLL-UHFFFAOYSA-N 0.000 description 1
- 229920000800 Acrylic rubber Polymers 0.000 description 1
- NLYNIRQVMRLPIQ-BVCZABNKSA-N Arteether Chemical compound C1C[C@H]2[C@H](C)CC[C@H]3[C@@H](C)[C@@H](OCC)O[C@H]4[C@]32OOC1(C)O4 NLYNIRQVMRLPIQ-BVCZABNKSA-N 0.000 description 1
- 101710018145 CLTC Proteins 0.000 description 1
- 101710019692 COR3 Proteins 0.000 description 1
- 210000001736 Capillaries Anatomy 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N Diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N Isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- CWOMTHDOJCARBY-UHFFFAOYSA-N N,N,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 1
- YQYUUNRAPYPAPC-UHFFFAOYSA-N N,N-diethyl-2-methylaniline Chemical compound CCN(CC)C1=CC=CC=C1C YQYUUNRAPYPAPC-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910004759 OSi Inorganic materials 0.000 description 1
- 101710019691 Olfr1 Proteins 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N Phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 229950000688 Phenothiazine Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N Pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 101700049711 SYCP3 Proteins 0.000 description 1
- 241000687904 Soa Species 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N Tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 101710008831 UQCRC1 Proteins 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000023298 conjugation with cellular fusion Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- YVHPHQBRUPLYOS-UHFFFAOYSA-N dichloromethane;methane Chemical compound C.ClCCl YVHPHQBRUPLYOS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- ZNNKQZCHFVLTNK-UHFFFAOYSA-N dipropyl pyridine-3,5-dicarboxylate Chemical compound CCCOC(=O)C1=CN=CC(C(=O)OCCC)=C1 ZNNKQZCHFVLTNK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 101700066013 dltC1 Proteins 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940052308 general anesthetics Halogenated hydrocarbons Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N methoxyethyl Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002943 quinolinyl group Polymers N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 101700024869 sor-3 Proteins 0.000 description 1
- 230000002269 spontaneous Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 230000021037 unidirectional conjugation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening Effects 0.000 description 1
Description
Activator Compositions for Cyanoacrylate Adhesives"
Field of the Invention
lliis invention relates to activator compositions, particularly well suited for accelerating the
hardening of cyanoacrylate adhesives. The invention also relates to novel mixtures of
chemical compounds and to the use of the activator compositions and the novel mixtures for
the accelerated hardening of cyanoacrylate adhesives. The invention further relates to a
process for the accelerated bonding of substrates using cyanoacrylate adhesives.
Briel‘ Description of Related Technology
Adhesive compositions based upon cyanoacrylate esters are well known and have found
extensive use, because of their rapid cure speed, excellent long-term bond strength, and
applicability to a wide variety of substrates. They generally harden after only a few seconds,
alter which the joined parts exhibit at least a certain degree of initial strength.
It is known that certain cyanoacrylate adhesives typically harden by an anionic polymeri-
sation reaction. However, with certain substrates, particularly substrates having acidic
surlaces, such as wood or paper, that polymerisation reaction may be retarded, oftentimes to
an unmanageable extent. Moreover, unless the adhesive is gelled or rendered thixotropic by
appropriate additives to confer such properties, the wood or paper substrates, due to their
porosity, tend to draw the adhesive out of the joint gap by capillary action before hardening
has taken place in the gap. If the adhesive is conventionally applied in a relatively thick layer
in the joint gap or relatively large amounts of adhesive are applied so that relatively large
drops of adhesive protrude from between the parts to be joined, rapid hardening throughout
may rarely be achieved.
I-leretolore efforts have been made to accelerate the polymerisation for such applications by
means of certain additives. Addition of accelerators directly to the adhesive formulation is
possible to only a very limited extent, however, since substances having a basic or
nucleophilic action, which would normally bring about a pronounced acceleration of the
polymerisation of the cyanoacrylate adhesive, are generally used at the expense of the storage
stability of such formulations.
Addition of such accelerators shortly before application of the adhesive results in virtually a
two—component system. However, such method has the disadvantage that the working life is
limited after the activator has been mixed in. In addition, with the small amounts of activator
that are required, the necessary accuracy of metering and homogeneity of mixing are difticult
to achieve. Moreover, use of such a two-component system is often seen as cumbersome to
the end user, and sometimes only modestly improves the intended result.
Activators are also used in the fomi of a dilute solution which is either sprayed beforehand
onto a substrate or part which is to be bonded, and/or is sprayed onto the adhesive where it is
still liquid after the substrates have been joined. The solvents used for such dilute solutions of
activators are generally low-boiling organic solvents, so that they may be readily evaporated,
leaving the activator on the substrate/part or the adhesive.
Japanese Patent Application No. .lP—A—62 022 877 proposes the use of solutions of lower
latty amines, aromatic amines, dimethylamine and the like. Japanese Patent Application No.
.ll’—A—l)3 207 778 proposes the use of solutions of aliphatic, alicyclic and, especially, tertiary
aromatic amines; particular examples which are mentioned are N,N-dimethylbenzylamine,
N-methylniorpholine and N,N—diethyltoluidine.
.lapanese Patent Application No. 59-66471 discloses a hardening accelerator for use with
cyanoacrylate adhesives comprising an amine compound, with a boiling point of between
50°C. and 25()°C., together with a deodorizer and a solvent. Examples of suitable amines are
triethyl amine, diethyl amine, butyl amine, isopropyl amine, tributyl amine, N,N-dimethyl
aniline, N,N—diethyl aniline, N,N-dimethyl-p—toluidine, N,N—dimethyl-m—toluidine, N,N-
dimcthyl-()-loluidine, dimethyl benzyl amine, pyridine, picoline, vinyl pyridine,
ethanolamine, propanolamine and ethylene diamine.
U.S. Patent No. 3, 260, 637 of von Bramcr discloses the use of a range of organic amines
(excluding primary amines) as accelerators for cyanoacrylate adhesives, particularly for use
on metallic and non—metallic substrates. N,N—dimethyl-p=toluidine has been widely used as
an accelerator for the accelerated hardening of cyanoacrylate adhesives. A crucial disadvan-
tage of the use of that substance is the short duration of the surface activation, which does not
permit long waiting times between application of the accelerator solution beforehand to the
substrates to be bonded and the subsequent bonding process. In addition, the use of N,N-
dimethyl-p-toluidine in some countries oftentimes involves rigorous regulatory labelling
requirements.
Basicity of an accelerator substance is not a sufficient criterion for identifying solutions
which are acceptable in practice in terms of application technology. Many substances, such as
alkylamines, 1,2—di—(4-pyridyl—ethane), 4,4'—dipyridyl disulfide, 3—(3-hydroxypropyl)pyridine,
l,2-bis(diphenylphosphino)-ethane, pyridazine, methylpyridazine or 4,4’-dipyridyl, are so
basic or nucleophilic that spontaneous superficial hardening takes place at the adhesive
interface (shock hardening) before the activator is able to initiate polymerisation throughout
the liquid adhesive layer by convection and diffusion. The result is that an often cloudy
polymerisation occurs at the surface only. With other compounds, such as oxazoles, the
basicity is evidently too low, and the hardening is often too slow for practical purposes.
German Patent DE—A—22 61 261 proposes accelerator substances containing the structural
element -N:(i?-S-, including 2,4-dimethylthiazole. However, that compound has a very high
volatility, so that activator solutions based thereon are unsuitable for application beforehand
since the active ingredient also evaporates offwith the solvent.
It is desired to find new activator compositions for use with cyanoacrylate adhesives, which
activator compositions have a pronounced accelerating action and low volatility, so that
application beforehand is also possible. It is also desired to find activators which are subject
to regulatory labelling requirements less rigorous than is N,N-dimethyl-p-toluidine currently.
Notwithstanding the state-of-the-art, it would be desirable to provide further activator
substances and combinations of activator substances with different properties from the
activator substances used up to now.
Summary of the Invention
The present invention provides an activator composition for the accelerated hardening of
cyanoacrylate adhesives, wherein the activator comprises a member selected from the group
consisting ol’:
aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and
substituted on the ring(s)with at least one electron - withdrawing group which decreases the
base strength of the substituted compound compared to the corresponding unsubstituted
compound,
mixtures of any of the foregoing with each other, and/or with N,N—dimethyl-p—toluidine,
and mixtures of any of the foregoing and/or N,N-dimethyl-p-toluidine with an organic
compound containing the structural element, -N=C-S—S—.
in the said organic compound containing the structural element —N=C-S-S-, the N=C double
bond may optionally be part ol‘ an aromatic system, which may suitably be monocyclic,
hicyclic or tricyclic. For example, the N=C double bond may suitably be part of an aromatic
heterocyclic ring having one or more N hetero atoms in the ring, optionally with one or more
other hetero atoms selected from S and O. The heterocyclic ring may be substituted.
Desirahly the said organic compound contains the structural element -N=C—S—S—C=N—, in
which case both the N=C double bond and the C:N double bond may optionally be part of
aromatic systems as described above, suitably two similar aromatic systems. More desirably
the said organic compound is selected from dibenzothiazyl disulfide, 6,6'—dithiodinicotinic
acid, 2,2’-dipyridyl disulfide, and bis(4-t-butyl-1~isopr0pylimidazolyl) disultide. Of
course, combinations of these organic compounds may also be used.
Desirably the activator comprises a member selected from the group consisting of pytidines,
quinolines and pyrimidines substituted on the ring(s) with at least one electron-withdrawing
group which decreases the base strength of the substituted compound compared to the
corresponding unsubstituted compound.
An aromatic heterocyelic compound may suitably be monocyclic, bicyclic or tricyclic. The
N hetero atoms(s) may be present in one or more of the rings. Two or more heterocyclic
rings may be fused, or a heterocyclic ring may be fused to one or more carbocyclic rings. A
heterocyclic ring may suitably be a 5- or 6-membered ring with one or two N—atoms in the
ring.
Suitably the at least one electron-withdrawing group is selected from the group consisting of
halo, CN, <:F_.,, coon, COR, OR, SR, CONR1R2,NO2, SOR, so2R3, SO3R3, PO(OR3)2 and
optionally substituted C6-C30 aryl, wherein R, R1 and R2 (which may be the same or different)
are H, optionally substituted C1-C10 alkyl, or optionally substituted C6-C20 aryl, and R3 is
optionally substituted C1—(Im alkyl, or optionally substituted C6-C30 aryl.
For example, the electron-withdrawing group may be selected from the group consisting of
halo, (IN, COOR and COR1.R, R1, R2 and R3 may suitably be optionally substituted C1-C5
alkyl, tor example unsubstituted (f‘,1~(iI5 alkyl.
'llic criterion that the electron-withdrawing group decreases the base strength of the
substituted compound compared to the corresponding unsubstituted compound may be
determined by pKa measurement in water under standard conditions (e.g. 25°C and zero
ionic strenvth b conventional means or usinv a software ackaoe which calculates Ka of
D D D
the base such as “ACD/pKa Calculator” available from Advanced Chemistry Development,
l33 Richmond Street West, Suite 605, Toronto, ON NSH ZLS, Canada.
According to a particular aspect, the activator is selected from:
pyridines having one or more electron—withdrawing groups in the 3-, 3,4- or 35- position in
the ring, suitably 3,5-dihalopyridines, such as 3,5-dichloropyridine or 3,5-dibromopyridine,
or 3-cyano pyridine, a lower alkyl 3,5— pyridine dicarboxylate, or a 5—halo nicotinic acid such
as 5-bromo nicotinic acid,
pyridines having an electron-withdrawing group in the 2 position in the ring, suitably a
COOR or COR group, such as 2-acetyl pyridine,
pyridines having an e1ectron—withdrawing group in the 4-position in the ring, suitably 4-
nitropyridine,
pyrimidines having an electron-withdrawing group in the 4- or 5-position on the ring,
suitably 4- or 5~halo pyrimidines, such as 4-bromopyrimidine or 5—bromopyrimidine,
nitroquinolines, suitably 5-nitroquinoline, polyhalogenated quinolines, suitably 4,7- dihalo
quinolines such as 4,7—dichloro quinoline,
and aromatic heterocyclic compounds which are substantially iso-electronic to any of the
fore going compounds.
According to one feature, the present invention provides an activator composition for the
accelerated hardening of cyanoacrylate adhesives, wherein the activator comprises a member
selected from the group consisting of:
aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and
substituted on the ring(s)with at least one substituent selected from the group consisting of
halo, (TN, C12,, COOR, COR, OR, SR, CONR1R2,NO3, SOR, sozti‘, so,Ri Po(oR“)3 and
optionally substituted C(,—C3(, aryl, wherein R, R1 and R2 (which may be the same or different)
are 1-1, optionally substituted (i1—Cm alkyl, or optionally substituted C6-C30 aryl, and R3 is
optionally substituted (I?]—(.'3m alkyl, or optionally substituted C6-C30 aryl,
mixtures of any of the foregoing with each other, and/or with N,N-dimethyl-p—toluidine,
and mixtures of any of the foregoing and/or N,N—dimethyl—p-toluidine with an organic
compound containing the structural element, -N=C-5 b
It is particularly desirable to use a mixture of activators in order to obtain a combination of
properties, some at least of which would not be expected.
According to a special feature, the present invention provides an activator composition for
the accelerated hardening of cyanoacrylate adhesives, wherein the activator comprises a
mixture of an aromatic heterocyclic compound as described above and an organic compound
having the structural element, -N:C-S-S-. According to a further feature, the present
invention provides an activator composition for the accelerated hardening of cyanoacrylate
adhesives, wherein the activator comprises a mixture of a 3,5-dihalopyridine and an organic
compound having the structural element, -N:C-S-S-.
According to another feature, the present invention provides a composition comprising a
mixture of:
(A) a member selected from the group consisting of:
aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and
substituted on the ring(s) with at least one electron - withdrawing group which decreases the
base strength of the substituted compound compared to the corresponding unsubstituted
compound,
N,N-dimethyl-p-toluidine,
and mixtures of any of the foregoing,
with
(B) an organic compound containing the structural element, -N:C-S-S-.
According to another feature, the present invention provides a composition comprising a
mixture ol’:
(A) a member selected from the group consisting of:
aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and
substituted on the ring(s) with at least one substituent selected from the group consisting of
halo, (TN, c::F_.,, o(oR~‘)3 and
optionally substituted C6-C30 aryl, wherein R, R1 and R2 (which may be the same or different)
are H, optionally substituted C1—C10 alkyl, or optionally substituted C6-C30 aryl, and R3 is
optionally substituted C1-Cm alkyl, or optionally substituted C6-C30 aryl,
N,N—dimethyl-p-toluidine,
and mixtures of any of the foregoing,
with
(B) an organic compound Containing the structural element, -N=C-S-S-.
According to one aspect, the present invention includes the use of a composition as defined
above for the accelerated hardening of a cyanoacrylate adhesive. The composition may be
applied to a substrate before application of the cyanoacrylate adhesive thereto, and/or the
composition may be applied to the cyanoacrylate adhesive after application of the adhesive to
a substrate.
According to a further aspect, the present invention provides an adhesive system comprising
a cyanoacrylate adhesive together with a composition as defined above. Suitably, the
composition as defined above is held separately from the adhesive prior to application on a
substrate.
According to another aspect, the present invention provides a process for the bonding of
substrates or parts, characterised by either of the following series of steps:
(a) dispensing an activator composition as defined above onto at least one
surface of the substrates or parts to be joined;
(b) optionally exposing solvent or other liquid vehicle in the activator
composition to air, optionally with heating or with the aid of a fan;
(d)
(6)
(ii)
(iii)
optionally holding the substrate or part having the activator
composition thereon for a retention or shipping period,
applying a cyanoacrylate adhesive to at least one substrate or part;
joining the substrates or parts, optionally with manual or mechanical
fixing,
optionally subsequently dispensing the activator composition onto
adhesive exposed from a joint gap;
applying a cyanoacrylate adhesive onto at least one surface of the
substrates or parts to be joined;
joining the substrates or parts, optionally with manual or mechanical
fixing;
dispensing an activator composition as delined above onto the adhesive
before or after the step of joining the substrates or parts,
optionally exposing solvent or other liquid vehicle in the activator
composition to air, optionally with heating or with the aid of a fan.
Suitably the retention or shipping period in step (c) may be in the range from several
minutes to several days, for example from two minutes to forty-eight hours. Optionally the
activator composition may be applied onto parts prior to their shipping, forwarding or
delivery to an end—user, customer or contractor.
The present invention includes a bonded assembly of substrates or parts bonded by a process
as defined above. The present invention also includes as an article of commerce a substrate or
part having a composition as defined above applied thereto.
Detailed Description of the Invention
An alkyl group may be straight—chained or branched and may be unsaturated, i.e. the term
alltyl as used herein includes alkenyl and alkynyl. A C1-Cm alkyl group may for example be
a (C31-(C15 alkyl group. A lower alkyl group may suitably be a C1-C5 alkyl group. An aryl group
includes plienyl and naphthyl groups, either of which may be substituted with an alkyl group,
more particularly a lower alkyl group. Halo includes chloro, bromo, fluoro and iodo, as well
as pseudohalo-radicals such as CN, SCN, OCN, NCO, NCS.
An optionally substituted alkyl, alkoxy or aryl group may be substituted with a substituent
selected from the group consisting of halo, CN, CF3, COOR, COR, OR, SR, CONRIR2,
N03, soa, sozn‘, so,R“, PO(OR3)3 and optionally substituted C6-C3) aryl, wherein R, R‘
and R3 (which may be the same or different) are H, optionally substituted C1-C10 alkyl, or
optionally substituted (?(,—CI3., aryl, and R3 is optionally substituted C1—C10 alkyl, or optionally
substituted (‘»{Y‘(::3() aryl.
In an organic compound containing the structural element -N:C—S—S—, in which the N=C
double bond is part of a heterocyclic ring, the heterocyclic ring may be substituted for
example with optionally substituted C1-C10 alkyl, optionally substituted C1-C10 alkoxy,
optionally substituted C1—(_‘/10 alkoxyalkyl, halo, CN, CF3, COOR, COR, OR, SR, CONR1R2,
N03, SOR, SOZR3, S()3R‘l, PO(OR3)3 and optionally substituted C6-C30 aryl or aryloxy,
(iIS(fi)R3, <;:ooNR‘3, NRCOOR, N=N-R3, oon‘, ssa‘, oocoR“, NOR33, ON(COR3)2, s-
aryl, NR2, SH, OH, SiR33, Si(OR3)3, OSiR33, OSi(OR3)3, B(OR3)3, P(OR3)2, SOR3, osiz‘,
wherein R,Rl and R2 (which may be the same or different) are H, optionally substituted C1-
(Tm alkyl, or optionally substituted (3(,—C_I3(, aryl, and R3 (which may be the same or different)
is optionally substituted C1-(Cm alkyl, or optionally substituted (I(,—(i33(, aryl.
Desirably, an activator composition comprises an amount of activator effective to accelerate
hardening ol‘ a cyanoacrylate adhesive, the activator being carried in a suitable vehicle.
Suitably the activator composition is an activator solution of the activator in a solvent.
Alternatively the composition may be a dispersion of the activator in a suitable vehicle,
particularly a liquid vehicle.
Desirably, the activator(s) are dissolved in readily volatile organic solvents, such as
hydrocarbons, carboxylic acid esters, ketones, ethers or halogenated hydrocarbons and
carbonic acid esters or acetals or ketals. The solutions of the activator(s) may suitably contain
the activator compound(s) in concentrations of from 0.01 to 10 g per 100 ml of solvent; for
example, from 0.05 to 5 g of activator substance are dissolved per 100 ml of solvent.
When the activator composition contains a mixture of two activator compounds, the
respective amounts of the activator compounds may vary and are only limited by respective
amounts which will no longer effective for the desired combination of properties. More
particularly, when the activator composition contains a mixture of an aromatic heterocyclic
compound substituted with at least one electron-withdrawing group and an organic
compound having the structural element —N=C—S—S—, the activator compounds may suitably
be present in amounts of about 0.1% to about 10% by weight of the said aromatic
heterocyclic compound and about 0.01% to about 5% by weight of the said organic
compound, more particularly about 0.05% to about 1%, of the said organic compound, based
on the total weight of the activator composition.
Various conventional organic solvents are suitable as solvents for the activator(s) according
to the present invention, provided they have a sufficiently high volatility. Desirably, the
boiling point of the solvent is below about 120°C, suitably below about 100°C, at ambient
pressure. Suitable solvents include specialized boiling point gasolines, but especially n-
heptane, n—bromopropane, alcohols, for example isopropyl alcohol, alkyl esters of lower
carboxylic acids, for example ethyl acetate, isopropyl acetate, butyl acetate, ketones, such as
acetone, methyl isobutyl ketone and methyl ethyl ketone. Also suitable are ether solvents,
ether esters or cyclic ethers, such as, especially, tetrahydrofuran. In the case of sparingly
-]2_
soluble activators, chlorinated hydrocarbons, such as dichloromethane or trichloromethane
(chloroform), may also be used.
'lhe activator compositions according to the present invention are suitable for the accelerated
hardening of conventional cyanoacrylate adhesives which contain as the fundamental
constituent one or more cyanoacrylic acid esters, inhibitors of free-radical polymerisation,
inhibitors of anionic polymerisation and, optionally, conventional auxiliary substances
employed in such adhesive systems, like fluorescence markers.
The cyanoacrylic acid esters used in the adhesives are in the main one or more esters of 2-
cyanoacrylic acid. Such esters correspond to the following general formula:
H3C=C(CN)—CO-O-R4.
In that formula, R4 represents an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or
haloalkyl or other suitable group, especially a methyl, ethyl, n—propyl, isopropyl, n-butyl,
isobutyl, pentyl, hexyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl,
2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl
or 2—ethoxyethyl group. The above-mentioned cyanoacrylates are known to a person skilled
in the art of adhesives, see Ullmann's Encyclopaedia of Industrial Chemistry, Volume A1, p.
240, Verlag (Themie Weinheim (1985) and U8. Patent Nos. 3,254,111 and 3,654,340.
Preferred monomers are the allyl, methoxyethyl, ethoxyethyl, methyl, ethyl, propyl,
isopropyl or butyl esters of 2—cyanoacrylic acid. The monocyanoacrylic acid esters represent
the largest proportion by weight of the polymerisable monomers in the adhesive.
The mentioned cyanoacrylic acid esters may suitably be present in the adhesives in amounts
of from 99.99 to 90 wt.%. Preference is given to cyanoacrylic acid esters the alcohol radical
of which is derived from alcohols having from 1 to 10 carbon atoms, which may also be
cyclic, branched or perlluorinated.
The cyanoacrylate adhesives according to the present invention may also contain an inhibitor
of free-radical polymerisation. Such inhibitors are, for example, hydroquinone, p-methoxy~
phenol, but also sterically—hindered phenols, phenothiazine and the like.
The cyanoacrylate adhesives according to the present invention may also contain thickeners
as further auxiliary substances. That is desirable especially when there are to be bonded
porous materials which otherwise readily absorb the low~viscosity adhesive. Many types of
polymer may be used as thickeners, such as polymethyl methacrylate, other methacrylate
copolymers, acrylic rubber, cellulose derivatives, polyvinyl acetate or
polyalphacyanoacrylate. A usual amount of thickener is generally about 10 wt.% or less,
based on the total adhesive. In addition to or instead of the thickeners, the cyanoacrylate
adhesives according to the present invention may also contain reinforcing agents. Examples
of such reinforcing agents are acrylic elastomers, acrylonitrile copolymers, elastomers or
fluoroelastomers. Moreover, inorganic additives may also be used, for example silicates,
thixotropic agents having a large surface area, which may be coated with polydi—
alkylsiloxanes.
The cyanoacrylate adhesives according to the present invention may also contain substances
for increasing the thermal stability thereof. There may be used for that purpose, for example,
the sulfur compounds mentioned in European Patent specification No. 579 476.
In addition to or instead of the mentioned additives, the cyanoacrylate adhesives according to
the present invention may also contain plasticisers. These serve to protect the resulting
adhesive bond from brittleness. Such plasticisers are, for example, C1—C10 alkyl esters of
dibasic acids, especially of sebacic acid, phthalic acid or malonic acid. Other plasticisers are
diaryl cthers and polyurethanes and the like. Furthermore, the adhesive preparations
according to the present invention may also contain colorings, pigments, aromatic substances,
extenders and the like, as well as tluorescing additives. Reference is directed to U.S.Patent
Nos. 5,74‘),.95() (Fisher et al.), 4,869,772 (McDonnell et al.) and 5,314,562 (McDonnell et
al.), the contents of which are incorporated herein by reference.
The activator compositions of the present invention are intended to be used with a wide
variety of both metallic and non—metallic substrates, including substrates having acidic
surfaces such as wood and paper or cardboard.
The present invention will now be illustrated in greater detail.
l€X/—\Ml’LES
In the Examples, the following abbreviations and terms are used:
DCP 2 3,5—dichloro pyridine, DBP = 3,5-dibromo pyridine,
NQ : 5-nitro quinoline DCQ = 4, 7—dichloro quinoline,
DPDS : 2,2’—dipyridy1 disulfide, BBID = Bis( 4-t-butyl-isopropylirnidazolyl)
disulfide,
DMPT = N,N-dimethyl—p—to1uidine, NBP : n-brornopropane,
Heptane = n-heptane, CTV = cure through volume
(f?Nl’ : 3-Cyano Pyridine
< 1% (TNP : Saturated solution of CNP in heptane, it was not fully soluble at 1%
concentration
Bl‘ : 5—bromo pyrimidine, ACP — 2-acetyl pyridine
l)l’Pl)(i? = Dipropyl 3, 5-Pyridine Dicarboxylate,
BNA : 5—hromo nicotinic acid in IPA solvent
IPA zisopropyl alcohol solvent, DIOX = 1,4-dioxane solvent
I-IP01. : heptanol solvent, DCB = 1,2—dichloro benzene solvent
Loctite 401, Loctite 411, Black Max/Loctite 380, Loctite 416 and Loctite 424 :
Different grades of Loctite ethyl cyanoacrylate-based adhesive
: Loctite 7457 (activator) 7455 = Loctite 7455 (activator).
Loctite 401 (also called 401 herein) is a low viscosity, fast curing, single component
ethyl cyanoacrylate adhesive (see for example U.S. Patent No. 4,695,615).
Loctite 411 (also called 411 herein) is a single component high viscosity ethyl
cyanoacrylate adhesive formulated for impact and peel resistance (see for example U.S.
Patent No. 4,477,607)
Black Max — Loctite 380 — is a black, rubber toughened ethyl cyanoacrylate adhesive
with enhanced resistance to peel and shock loads (see for example U.S. Patent No.
,44o, 91(1).
Loctite 424 is an ethyl cyanoacrylate adhesive particularly for bonding EPDM and other
similar elastomers.
Loctite 416 is a high viscosity ethyl cyanoacrylate adhesive for bonding rubbers, plastics
and metals.
Loctite 7455 is a single component surface activator based on DMPT in heptane.
Loctite 7457 is another single component surface activator based on poly(oxypropylene)
diamine in heptane.
Loctite is a trade mark. The above Loctite products are commercially available from
Loctite Corporation, Rocky Hill, Conn., USA or Loctite (Ireland) Limited, Dublin 24,
Ireland.
Example 1
Post Spray tests were carried out by applying a 10 pl drop of adhesive onto a substrate
and then spraying a chosen activator onto the drop. Full Cure Time is the time required
for the adhesive drop to cure fully.
.16.
In Pre Spray tests the selected activator solution is sprayed onto the substrate before
application of a 10 Ml drop of adhesive. On Part Time is the time interval between
application of the spray and addition of the adhesive drop.
The Post Spray cure speeds of a range of activators are shown in table 1. DCP, DBP and
(TN P provided faster Post Spray cure times than DMPT with Loctite 401 adhesive on a
cardboard substrate, although good CTV performance was also obtained from the other
activators listed.
Table 1
Post spray full cure times of various activators in heptane solvent for
a 10 pl drop of401 adhesive on a cardboard substrate.
Activator Cone (%) Full CureTime (s)
DMPT 1 15
DCP 1 10
DBP 1 12.5
CNP* <1 6
NO 3 7.5
DCQ 3 30
DPPD 1 30
BP 1 40 -45
AC? 1 60
BNA+ 1 195
*saturated solution in heptane was not fully soluble at 1% Cone.
+ IPA solvent
Table 2 compares the Post Spray performance of DCP and DBP with that of DMPT for
various adhesive grades on cardboard and mild steel substrates. 3% levels of DCP were
required to match the cure speed of 1% DCP on a mild steel substrate. Similarly 3%
levels of DCP and DBP were required to match the cure speed of DMPT with higher
viscosity Black Max and 411 grades of adhesive on a cardboard substrate.
The difference in Post Spray cure speed of both DCP and DMPT with a fresh and less
active aged sample of 401 on a cardboard substrate is shown in table 2. It is evident that
DCP levels of ~ ().75% provided similar cure speeds to 1% DMPT for both the fresh and
aged adhesive.
Table 2
Post Spray skin and full cure times ofvarious activators in heptane solvent for a range of
different adhesive grades with 10 ul drop of adhesive on cardboard and mild steel substrates.
Activator Conc (%) Adhesive Substrate Skin Time Full Cure Time
(seconds) (seconds)
DMPT 1.0 Aged 401 Cardboard nm 20-25
“ 1.0 Fresh 401 “ “ 15
DCP 0.25 Aged 401 ' “ “ 50
“ 0.5 “ “ “ 30
0.75 “ “ “ 20
1.0 “ “ “ 15
0.25 Fresh 401 “ ii 3()
0.5 “ “ “ 20
0.75 “ “ “ 15
1.0 “ “ “ 10
“ 3.0 “ “ “ 7.5
DBP 1.0 “ “ “ 12.5
“ 3.0 “ “ “ 7.5
DMPT 1.0 411 “ 15 25
DCP 1.0 “ “ 15-20 45
3.0 “ “ 15 25
DB? 1.0 “ “ 15 45
“ 3.0 “ “ 15 25
DMPT 1.0 Black Max “ 30 150
DCP 1.0 “ “ 40 210
“ 3.0 “ “ 30 120
DBP 1.0 “ “ 75 225
“ 3.0 “ “ 30 135
DMPT 1.0 40] Mild Steel nm 7.5
DCP 1.0 “ “ “ 20
“ 2.0 “ “ “ 15
3.0 “ “ 7.5
(nm = not measured)
The Pie Spray cure speed of DCP, DB1’, DCQ and NO on a cardboard substrate is
compared with DMPT in table 3. The results show that 3% levels of DCP were
required to match the “On Part Time” performance of 1% DMPT. The
performance of 1% DBP was closely similar to that of 1% DMPT. A notable
feature of the results is the good long term “On Part Time” performance of DB1’,
NO and DBP at 3% levels. NO in particular showed no change in its curing
behaviour even after an “On Part Time” of 24 hours. The beneficial effect of
adding 10% of high boiling point solvents to 2 and 3% DCP in heptane is also
illustrated in table 3.
Table 3
Effect ofdifferent activators, activator concentration, solvent and activator “On Part Time” on the
Pre Spray skinning and full cure time of a 10 [Al drop of 401 adhesive on a cardboard substrate.
The solvent is heptane unless otherwise indicated.
Activator Cone. (%) Co Solvent On Part Time Skin Time Full Cure Time
(minutes) (minutes) (minutes)
1)Ml"l‘ 1.0 None 1 0.3 -0.5 10-125
“ “ “ 15 1.5 2.75
“ 60 5.0 7.0
“ 180 9.0-9.5 12.0
l)Cl’ “ “ 1 1.0 2.0
" “ “ 15 4.0 7.0-7.5
“ 60 7.0 10.5
.0 “ 1 1.0 2.0
“ 15 3.5 6.0
“ 60 6.0 9.5
.0 “ 1 0.17 0.6
“ “ 15 0.75 1.5
‘T “ 60 3.5 6.0
“ 180 7.5 11.0
.0 10% DIOX 1 0.08 -0.16 0.25
“ 15 1.5 2.25
“ 60 3.5 6.0
“ 180 8.0 8.5
.0 10% HPOL 1 0.08 -0.16 0.3
“ “ 15 1.25 1.5
“ 30 2.75 4.75
“ 60 3.0 5.0
.5 8.5
DB1’ 1.0 none 1 0.3 0.5
“ “ “ 15 “ 4.75
7.5
“ 60 “ 15
.0 “ i 1 0.08 -0.16 0.25
“ “ 15 “ ().25
" 30 “ 0.25
.3 2.5
“ 120 2.5 5.5
“ 180 12 17
DCQ 1.0 none 1 — 10.0
“ 2.() “ 1 3.0 5.0
“ 15 4.5 6 0
“ 30 4.5 6.0
“ 60 5.0 6.0
.0 7.5
% [PA
The effect of high boiling point solvents on the Pre Spray performance of 1% DCP is
illustrated in table 4. DCB and HPOL were particularly beneficial compared to the
equivalent results with heptane solvent (c.f. table 3).
Table 4
Effect of high boiling point solvents on the Pre Spray performance of
1% DCP with a 10 ill drop of 401 adhesive on a cardboard substrate.
The Pre Spray cure speed of DMPT, DCP and NQ on a mild steel substrate are
compared in table 5. Mild steel was a slower substrate than cardboard (c.f. table 3). As
already found with cardboard, 3% levels of DCP were required to match the
performance of 1% DMPT. Again NQ showed no change in its curing behaviour even
after an “(.)n Part Time” of 24 hours.
Table 5
Comparison of Pre Spray activator (DMPT, DCP and NQ) “On Part Time”
versus full cure time for a 10 pl drop of 401 adhesive on a mild steel substrate.
Activator Conc. (%) On Part Time Skin Time Full Cure
(minutes) (minutes) Time
(minutes)
I)lVIl’T 1.0 1 2 5
“ -~ 15 5 30-35
DCP 3.0 1 2 5
-‘ -‘ , 5 30-35
NQ 3.0 15 10 13
.. .. 30 .. ..
60 “ “
120 “ “
180 “ “
240 “ “
1440 “ “
It will be seen from the test results that the activator solutions according to the invention
have comparable or better properties than equivalent DMPT solutions.
Example 2
Tables GA and 6B show the results of a series of tests carried out with Loctite 424. The
various activators and their concentrations in the designated solvents are set out in Table
6/\. This Table also includes the results for tests for the Fixture time on mild steel lap
shears. The activator solution is applied to one of the lap shears and time is then allowed
to elapse before adhesive is applied onto the other mating part and the overlapping lap
shears are squeezed together so that the adhesive forms a thin layer. The time periods at
the heading of each column of results indicate the time span between application of the
activator solution and the bringing together of the lap shears i.e. one minute, two hours
or twenty—four hours. The fixture times are indicated in many cases as a range, the
lower figure indicating the time at which the lap shears were not fixed and the higher
figure indicating the time by which the lap shears were already fixed. The actual fixture
time would therefore lie in the range indicated.
Fig 6B. gives further results of tests on the same Compositions Nos. 1 to 42 as set out in
Table oA. “Pre Activation” and “Post Activation” tests are fillet cure tests carried out
on cardboard. In “Pre Activation” tests one drop of activator solution is applied onto
cardboard, then one drop of adhesive is applied onto the activator, either immediately
after the solvent has been evaporated from the activator solution or after waiting for an
additional period of fifteen seconds thereafter. The adhesive is left to cure without a
second substrate being applied to it. The cure time (in minutes) is measured by testing
the adhesive fillet with a spatula. Curing (hardening) is obtained when the fillet is
thoroughly solid.
In “Post Activation” tests, one drop of adhesive is applied to the cardboard substrate, and
one drop of activator solution is then applied to the adhesive. Again the fillet of
adhesive is left to cure without application of a second substrate. In the columns of
results, the heading “Whiten.” indicates whitening of the surface, which is generally
regarded as undesirable. “Crater.”, indicates cratering (uneven surface), which is also
undesirable. These two “cosmetic” effects are important physical parameters in
determining whether a commercial adhesive will be generally accepted by end users.
The column headed “Skin” indicates the time in seconds up to the appearance of skin
formation on the adhesive. This is judged visually by a change of the shine on the
surface. The column headed “Through” indicates the time in minutes up to full cure
through the fillet of adhesive. This is checked by pressing with a spatula.
Tensile shear strength on grit blasted mild steel was tested by standard methods. The
. . . 2
results given in the column headed “TSS” are in N/mm .
Tests 1 to 11 show the use of an activator composition containing DPDS alone, and test
12 shows an activator composition based on BBID alone. These tests are not within the
scope of the present invention. Tests 13 to 22 relate to an activator composition
containing DCP alone and test 23 concerns a composition containing DBP alone. These
compositions are in accordance with the invention. Test 24 is a comparative test using a
DMPT solution of the prior art. Tests 25, 26 and 27 are also comparative tests using the
commercially available activator composition Loctite 7457. Test 27A is another
comparative test using the commercially available activator composition Loctite 7455.
Tests 28 to 42 use compositions based on combinations of activators in accordance with
a special feature of the present invention.
The columns at the left hand edge of Table 6A facilitate comparison of the respective
test results. Reviewing the key in columns a— k it will be seen that the marking in
column a shows that test 28 relates to a combination of activators as used in tests 1 and
. Likewise column b indicates that test 29 relates to a combination of the activator
solutions used in tests 2 and 16 (NBP as solvent). The coding continues through to
columns e to k in a similar manner.
The tests results in Table 6A and 6B are to be compared overall, taking account of the
cosmetic effects as well as the technical data. It will be seen with reference to test 24
that the control example using DMPT shows a marked loss of fixture speed when there
is a twenty-four hour time span between application of the activator solution and
bringing together of the lap shears. There is also significant fixture speed loss with the
use of 7457 and 7455. It will be seen by reference to tests 1 to 12 that when DPDS or
BBID are used, that these activators have a pronounced accelerating action and almost
no loss of surface activation. DCP and DBP, on the other hand, have relatively slow
fixture times in this adhesive composition (Loctite 424).
Tables 7 and 8 show test results similar to those in Table 6B for activator compositions
26 and 28-37 but using Loctite 416 cyanoacrylate adhesive (Table 7) and Loctite 380
cyanoacrylate adhesive (Table 8).
When a combination of activators is used, particularly with formulations 28 to 41, it
will be seen from the test results that good accelerating action and almost no loss of
surface activation (e.g. after 24 hours) are achieved. ln addition, the test results shown
in Table 6B for the compositions containing combinations of activators are generally
favourable as compared to those for DPDS or BBID alone. In particular, in the “Pre
Activation” tests, the cure times for the combined activator compositions of tests 28 to
42 are generally significantly shorter than those for the comparable tests using DPDS or
BBID alone.
Likewise, in the “Post Activation” tests the “cosmetic effects” are generally favourable
in tests 28 to 42, and the Skin times and Through times are relatively short.
As seen, promising results have been found with combinations of DPDS and DCP.
The formulations 28-41 in particular show the following combination of properties:
. No or no substantial loss of surface activation.
. Fast cure after pre—activation.
. No or no substantial shortcomings in cosmetics.
4. Fast through cure after part activation.
. No or no substantial loss of bond strengths.
Activator solutions according to this invention allow manufacturers to have long waiting
periods between the steps of application of activator (surface activation) and application
of adhesive (bonding parts).
.24.
Thus the invention can confer the following benefits:
— lnterruptions / breaks / hold-ups in production lines do not require repeated surface
activation of the parts to be adhered.
— Parts to be bonded can be activated in advance by the supplier or a contractor. This
could be advantageous if manufacturer does not want to equip his production lines
with activator application stages.
— Large number of parts can be pre-treated in advance and be held in stock.
(floniparative tests described above are carried out using commcrcia1ly—available
adhesive compositions but the individual nature of these adhesive compositions is not
essential to the disclosure of the invention. The behaviour of activators is to be
compared within each test in relation to a particular adhesive composition and not from
test to test in different adhesive compositions.
Although the invention has been described above, many modifications and equivalents
thereof will be clear to those persons of ordinary skill in the art and are intended to be
covered hereby, the true spirit and scope of the invention being defined by the claims.
in (W/V)
DPDS
.05%
0.05%
0.15%
0.15%
0.15%
0.20%
0.20%
0,45%
0.45%
0.45%
0.45%
.05%
0.05%
0.05%
0.05%
0.10%
0.10%
0.15%
0.15%
0.15%
0.15%
.15%
.15%
_25_
Con1 ifion
Activator
BBID DCP DBP DMPT 7457
h
NBP
NBP
h
NBP
h
NBP
Solvent 1min
Fixture
Ms
2h
e 5-10
-15
e4
e4
e 4-5
-20
- 50
50- 55
- 20
40 -50
- 15 25 25
1035 25-
- 10
90- 100
60 -
80- 90
-
-26..
IABLEGB
Pre-Activ. [min] Post-Activation TSS
155 after [s] [min]
immed. d Whiten. Crater. Skin
6 trace trace 9 17.7 18.6
S no 4 — 5
12 trace trace
23 no trace
40 no no
no no
no
23 trace
no
45 no no
11 no no
.bChI--k.Dr-4uJbJL»JI—-
‘O N
U‘!
NJ
Ln
no no
no [10
>--
moo
I10 no
no I10
no no
H0 H0
no
no
HO
4
4
2
3
4
2
3
On)
Us.)
:
-5
u
U‘!
severe
severe
severe
trace
no
I
U)
HNNNAHANHNNNNN
D-5!)-4
N
['10
(Loctite7457)
Pre Activ. Post-Activation
No. 155 after [s] [min]
drying [min] Whiten. Crater. Skin Through
severe slightly 10 1 - 2
no slightly 20 1 - 2
no slightly 15 0.5
no slightly 15 1
no slightly 10 0.5
no slightly . 10 0.5
no slightly 10 0.5
no slightly 20 1 - 2
no slightly 10 0.5
no slightly 15 1
no slightly 15 0.5
..28_
Table 8
Pre Activ. Post-Activation
No. 155 after [5] [min]
cl min Whiten. Crater. Skin Thro h
(Loctite745 7) 27 severe 3
no
23 no
no
16 no
12 no
no
26 no
13 no
11 no
no
CJIDIDIDCIECIKDIDD
Claims (1)
- Claims: An activator composition for the accelerated hardening of cyanoacrylate adhesives, wherein the activator comprises a mixture of: (A) a member selected from the group consisting of: aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and substituted on the ring(s)with at least one electron - withdrawing group which decreases the base strength of the substituted compound compared to the corresponding unsubstituted compound, N,N-dimethyl—p-toluidine, and mixtures of any of the foregoing, with (B) an organic compound containing the structural element, —N=C-S—S-. A composition according to claim l wherein said organic compound (B) contains the structural element, -N=C-S—S—C=N—. A composition according to claim 2 wherein said organic compound (B) is selected from the group consisting of dibenzothiazyl disulfide, 6,6‘-dithiodinicotinic acid, 2,2‘-dipyridyl disulfide, and bis(4-t-butyl-1—isopropyl-2—imidazolyl) disulfide. A composition according to any of claims 1-3 wherein the activator comprises a member (A) selected from the group consisting of pyridines, quinolines and pyrimidines substituted with at least one electron-withdrawing group which decreases the base strength of the substituted compound compared to the corresponding unsubstituted compound. A composition according to claim 1 or 4 wherein the at least one electron- withdrawing group is selected from the group consisting of halo, CN, CF3, COOR, COR, OR, SR, coNR‘R2, N02, SOR, so2R3, SO3R3, PO(OR3)2 and optionally substituted Cs-C20 aryl, wherein R, R’ and R2 (which may be the same or different) are H, optionally substituted C1—C10 alkyl, or optionally substituted Ce-C20 aryl, and R3 is optionally substituted C1-C10 alkyl, or optionally substituted C6-C20 aryl. A composition according to claim 5 wherein the electron—withdrawing group is selected from the group consisting of halo, CN, COOR and COR wherein R is C1- C5 alkyl. A composition according to at least one of claims 1-6 wherein the activator comprises at least one member selected from the group consisting of 3,5 dihalopyridines, 3-cyano pyridine, lower alkyl 3,5-pyridine dicarboxylates, 5—halo pyrimidines, 2—acety1 pyridine, 5-halo nicotinic acids, 5—r1itro quinoline, 4,7-dichloro quinoline and 2—acetyl pyridine. A composition according to claim 7 wherein the 3,5—dihalopyridine is selected from the group consisting of 3,5—dichloropyridine or 3,5—dibromopyridine. A composition according to at least one of claims 1-8 wherein the composition is a solution of the mixture of compounds in a solvent. A composition according to claim 9 wherein an organic solvent selected from the group consisting of volatile hydrocarbons, alcohols, carboxylic acid esters, ketones, ethers, halogenated hydrocarbons, ketals, acetals or carbonic acid esters is used as solvent for the mixture. A composition according to claim 9 or 10 wherein the activator concentration is from 0.01 to 10 g, preferably from 0.05 to 5 g, of the mixture of compounds per 100 ml of solvent. A composition according to at least one of claims 1-11 wherein the compounds are present in amounts of about 0.1% to about 10% by weight of (A) the said aromatic heterocyclic compound and/or N,N—dimethyl—p—toluidine and about 0.01 % to about 5 % by weight of the (B) said organic compound, based on the total weight of the composition. An activator composition for the accelerated hardening of a cyanoacrylate adhesive throughout the adhesive, wherein the activator comprises a member selected from the group consisting of: aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and substituted on the ring(s) with at least one electron - withdrawing group which decreases the base strength of the substituted compound compared to the corresponding unsubstituted compound wherein said at least one electron-withdrawing group is selected from the group consisting of halo, CN, CF3, COOR, COR, OR, SR, CONR‘R2, NO2, SOR, SO2R3, SO3R3, PO(OR3)2 and optionally substituted C6-C20 aryl, wherein R, R‘ and R2 (which may be the same or different) are H, optionally substituted C1—C10 alkyl, or optionally substituted Cs-C20 aryl, and R3 is optionally substituted Cl-C10 alkyl, or optionally substituted C6—C20 aryl, mixtures of any of the said aromatic heterocyclic compounds with each other, and/or with N,N- dimethyl-p-toluidine, and mixtures of any of the said aromatic heterocyclic compounds and/or N,N—dimethyl—p—toluidine with an organic compound containing the structural element, —N =C-S—S—. An activator composition according to claim 13 wherein said organic compound contains the structural element, —N = C-S—S-C = N-. An activator composition according to claim 14 wherein said organic compound is selected from the group consisting of dibenzothiazyl disulfide, 6,6'—dithiodinicotinic acid, 2,2‘-dipyridyl disulfide, and bis(4-t-butylisopropylimidazolyl) disulfide. An activator composition according to any of claims 13-15 wherein the activator comprises a member selected from the group consisting of pyridines, quinolines, pyrimidines and pyrazines substituted with at least one electron-withdrawing group which decreases the base strength of the substituted compound compared to the corresponding unsubstituted compound. An activator composition according to any one of claims 13 to 16 wherein the said electron-withdrawing group is selected from the group consisting of halo, CN, COOR and COR wherein R is optionally substituted‘ C1-C5 alkyl. An activator composition according to at least one of claims 13-17 wherein the activator comprises at least one member selected from the group consisting of 3,5- dihalopyridines, 3—cyano pyridine, lower alkyl 3,5-pyridine dicarboxylates, 5—halo pyrimidines, 2-acetyl pyridine, 5—halo nicotinic acids, 5—nitro quinoline and 4,7- dichloro quinoline. An activator composition according to claim 18 wherein the 3,5—dihalopyridine is selected from the group consisting of 3,5-dichloropyridine and 3,5-dibromopyridine. An activator composition according to at least one of claims 13-19 wherein the composition is an activator solution of the activator in a solvent. An activator composition according to claim 20 wherein an organic solvent selected from the group consisting of volatile hydrocarbons, carboxylic acid esters, ketones, ethers, halogenated hydrocarbons, ketals, acetals or carbonic acid esters is used as solvent for the activator. An activator composition according to claim 20 or 21 wherein the activator concentration is from 0.01 to 10 g, preferably from 0.05 to 5 g, of activator per 100 ml of solvent. Use of an activator comprising a member selected from the group consisting of: aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and substituted on the ring(s) with at least one electron — withdrawing group which decreases the base strength of the substituted compound compared to the corresponding unsubstituted compound, mixtures of any of the said aromatic heterocyclic compounds with each other, and/or with N,N-dimethyl—p-toluidine, and mixtures of any of the said aromatic heterocyclic compounds and/or N,N—dimethyl-p—toluidine with an organic compound containing the structural element, -N = C-S-S- in the manufacture of an activator composition for the accelerated hardening of a cyanoacrylate adhesive throughout the adhesive. An activator composition for the accelerated hardening of cyanoacrylate adhesives, wherein the activator comprises a mixture of a 3,5—dihalopyridine and an organic compound having the structural element, —N =C—S—S—. An activator composition according to claim 24 wherein the activator compounds are present in amounts of about 0.1% to about 10% by weight of the 3,5- dihalopyridine and about 0.01 % to about 5% by weight of the said organic compound, based on the total weight of the activator composition. A composition comprising a mixture of a 3,5—diha1opyridine and an organic compound having the structural element, —N =C—S—S—. A composition according to claim 26 comprising a mixture of a 3,5-dihalopyridine and an organic compound having the structural element, —N=C—S-S—C=N— wherein the N=C and C =N double bonds are parts of aromatic heterocyclic rings. A composition according to claim 26 or 27 comprising a mixture of 3,5- dichloropyridine and 2,2’-dipyridyl disulfide. An activator composition for the accelerated hardening of cyanoacrylate adhesives, wherein the activator comprises a member selected from the group consisting of: aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and substituted on the ring(s)with at least one substituent selected from the group consisting of halo, CN, CF3, COOR, COR, OR, SR, CONR'R2, NO2, SOR, SO2R3, SO3R3, PO(OR3)2 and optionally substituted C6-C20 aryl, wherein R, R1 and R2 (which may be the same or different) are H, optionally substituted Ci-Cio alkyl, or optionally substituted C6—C20 aryl, and R3 is optionally substituted C1-C10 alkyl, or optionally substituted C6—C20 aryl, mixtures of any of the said aromatic heterocyclic compounds with each other, and/or with N,N—dimethyl—p-toluidine, and mixtures of any of the said aromatic heterocyclic compounds and/or N,N—dimethyl—p—toluidine with an organic compound containing the structural element, -N=C-S-S—. A composition comprising a mixture of: (A) a member selected from the group consisting of: aromatic heterocyclic compounds having at least one N hetero atom in the ring(s) and substituted on the ring(s)with at least one substituent selected from the group consisting of halo, CN, CF3, COOR, COR, OR, SR, CONR‘R2, NO2, SOR, SO2R3, SO3R3, PO(OR3)2 and optionally substituted C6—C20 aryl, wherein R, R‘ and R2 (which may be the same or different) are H, optionally substituted Cl-C10 alkyl, or optionally substituted C6-C20 aryl, and R3 is optionally substituted Ci—C1o alkyl, or optionally substituted C6-C20 aryl, N ,N—dimethyl—p—toluidine, and mixtures of any of the foregoing, with (B) an organic compound containing the structural element, —N=C-S-S-. Use of a composition according to at least one of the preceding claims for the accelerated hardening of a cyanoacrylate adhesive. Use according to claim 31 wherein the composition is applied to a substrate before application of the cyanoacrylate adhesive thereto. Use according to claim 31 or 32 wherein the composition is applied to the cyanoacrylate adhesive after application of the adhesive to a substrate. An adhesive system comprising a cyanoacrylate adhesive together with a composition according to at least one of claims 1-30. An adhesive system according to claim 34 wherein the composition according to at least one of claims 1-30 is held separately from the adhesive prior to application on a substrate. A process for the bonding of substrates or parts, characterised by either of the following series of process steps: (a) dispensing an activator composition according to any of claims 1-30 onto at least one surface of the substrates or parts to be joined; (b) optionally exposing solvent or other liquid vehicle in the activator composition to air, optionally with heating or with the aid of a fan; optionally retaining the substrate or part having the activator composition thereon for a retention or shipping period; applying a cyanoacrylate adhesive to at least one substrate or part; joining the substrates or parts, optionally with manual or mechanical fixing, optionally subsequently dispensing the activator composition onto adhesive exposed from a joint gap; applying a cyanoacrylate adhesive onto at least one surface of the substrates or parts to be joined; joining the substrates or parts, optionally with manual or mechanical fixing; dispensing an activator composition according to any of claims 1-30 onto the adhesive before or after the step of joining the substrates or parts, optionally exposing solvent or other liquid vehicle in the activator composition to air, optionally with heating or with the aid of a fan. A bonded assembly of substrates or parts bonded by a process according to claim 36. A substrate or part having a composition according to at least one of claims 1-30 applied thereto.
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IE2000/0367A IE83707B1 (en) | 2000-05-12 | Activator compositions for cyanoacrylate adhesives | |
JP2001582453A JP2003532779A (en) | 2000-05-12 | 2001-05-11 | Activator composition for cyanoacrylate adhesive |
US10/276,287 US6995227B2 (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives |
CN01810490A CN1432053A (en) | 2000-05-12 | 2001-05-11 | Activator compsns. for cyanoacrylate adhesives |
AT01928173T ATE308598T1 (en) | 2000-05-12 | 2001-05-11 | ACTIVATOR COMPOSITIONS FOR CYANACRYLATE ADHESIVES |
PCT/IE2001/000063 WO2001085861A1 (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives |
MXPA02011145A MXPA02011145A (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives. |
EP01928173A EP1280866B1 (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives |
KR1020027015171A KR20040030167A (en) | 2000-05-12 | 2001-05-11 | Activator Compositions For Cyanoacrylate Adhesives |
CA002408512A CA2408512A1 (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives |
AU55035/01A AU5503501A (en) | 2000-05-12 | 2001-05-11 | Activator compositions for cyanoacrylate adhesives |
DE60114605T DE60114605T2 (en) | 2000-05-12 | 2001-05-11 | ACTIVATOR COMPOSITIONS FOR CYANACRYLATE ADHESIVES |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IE2000/0367A IE83707B1 (en) | 2000-05-12 | Activator compositions for cyanoacrylate adhesives |
Publications (2)
Publication Number | Publication Date |
---|---|
IE20000367A1 IE20000367A1 (en) | 2002-12-11 |
IE83707B1 true IE83707B1 (en) | 2004-12-15 |
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