GB2580162A - One-part photocurable (METH) acrylate compositions - Google Patents
One-part photocurable (METH) acrylate compositions Download PDFInfo
- Publication number
- GB2580162A GB2580162A GB1821125.0A GB201821125A GB2580162A GB 2580162 A GB2580162 A GB 2580162A GB 201821125 A GB201821125 A GB 201821125A GB 2580162 A GB2580162 A GB 2580162A
- Authority
- GB
- United Kingdom
- Prior art keywords
- borane
- photocurable composition
- composition according
- styrene
- meth
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 39
- -1 polyethylene Polymers 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 claims abstract description 22
- 229920001155 polypropylene Polymers 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 17
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000098 polyolefin Polymers 0.000 claims abstract description 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 12
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- JYKHAJGLEVKEAA-UHFFFAOYSA-N 2-(hydroxymethyl)anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CO)=CC=C3C(=O)C2=C1 JYKHAJGLEVKEAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012965 benzophenone Substances 0.000 claims abstract description 10
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims abstract description 10
- SNVTZAIYUGUKNI-UHFFFAOYSA-N dibenzo[1,2-a:1',2'-e][7]annulen-11-one Chemical compound C1=CC2=CC=CC=C2C(=O)C2=CC=CC=C21 SNVTZAIYUGUKNI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010547 Norrish type II reaction Methods 0.000 claims abstract description 7
- GRDGBWVSVMLKBV-UHFFFAOYSA-N (2-amino-5-nitrophenyl)-(2-chlorophenyl)methanone Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C(=O)C1=CC=CC=C1Cl GRDGBWVSVMLKBV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 claims abstract description 5
- SJKKMGRHBRUPIG-UHFFFAOYSA-N 3-methoxypropan-1-amine;tributylborane Chemical compound COCCCN.CCCCB(CCCC)CCCC SJKKMGRHBRUPIG-UHFFFAOYSA-N 0.000 claims abstract description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960000956 coumarin Drugs 0.000 claims abstract description 5
- 235000001671 coumarin Nutrition 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- IJUCBZFJEAVADL-UHFFFAOYSA-N propane-1,3-diamine;triethylborane Chemical compound NCCCN.CCB(CC)CC IJUCBZFJEAVADL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000013011 mating Effects 0.000 claims abstract description 3
- LRIOGIBXOOAGMT-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;triethylborane Chemical compound CCB(CC)CC.NCCNCCN LRIOGIBXOOAGMT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910000085 borane Inorganic materials 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical group CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 4
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 abstract 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 abstract 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 31
- 230000001070 adhesive effect Effects 0.000 description 31
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 27
- 150000003254 radicals Chemical group 0.000 description 16
- 239000000463 material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000010546 Norrish type I reaction Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000012949 free radical photoinitiator Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
- OGJDNTCMTVTFAS-UHFFFAOYSA-N trioctylborane Chemical compound CCCCCCCCB(CCCCCCCC)CCCCCCCC OGJDNTCMTVTFAS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- HWWBSHOPAPTOMP-UHFFFAOYSA-N tritert-butylborane Chemical compound CC(C)(C)B(C(C)(C)C)C(C)(C)C HWWBSHOPAPTOMP-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/143—Glass in the substrate
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- C09J2400/20—Presence of organic materials
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- C09J2400/00—Presence of inorganic and organic materials
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- C09J2400/226—Presence of unspecified polymer in the substrate
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- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
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Abstract
A one-part photocurable composition comprises a (meth)acrylate component, a Norrish type II photoinitiator, and a borane-amine component. The borane-amine component may be present in an amount of 1-15 wt.% and may be an organoborane-amine complex, such as triethylborane-1,3-diaminopropane, tributylborane-3-methoxypropylamine, or triethylborane-diethylenetriamine. The photoinitiator is preferably benzophenone, chlorobenzophenone, methylbenzophenone, dimethylaminobenzophenone, 4,4’-bis(dimethylamino)benzophenone, 5-dibenzosuberenone, xanthone, benzil, anthraquinone, 2-(hydroxymethyl)anthraquinone, 2-methylanthraquinone, or coumarin. The composition may comprise 1-20 wt.% toughener, e.g. SIS, SBS, SIBS, SEBS, and SEPS. A method of bonding two substrates is also disclosed, which comprises applying the composition to at least one substrate, mating the substrates together, and exposing the composition to radiation having a wavelength of 200-700 nm to effect curing. At least one substrate may have a low energy bonding surface and may be formed of glass or plastics, such as a polyolefin like polyethylene or polypropylene.
Description
ONE-PART PHOTOCURABLE (METH) ACRYLATE COMPOSITIONS
BACKGROUND
Field
[0001] The present invention relates to (meth)acrylate-based polymerizable compositions and adhesive systems prepared therefrom, which include an organoborane component. The inventive compositions and adhesive systems are particularly well suited for bonding applications, which involve at least one low energy bonding surface, for example, polyolefin surfaces, such as polyethylene and polypropylene.
Brief Description of Related Technolopy
[0002] Low energy surfaces such as polyolefins, e.g., polyethylene, polypropylene, polybutene, polyisoprene, and copolymers thereof, are well known to be difficult to bond to each other and to other surfaces using adhesive bonding technology since they have few active bonding sites available at the free surfaces. Low energy surfaces typically have surface energy values of less than 45 mJ/m2, more typically less than 40 mJ/m2, such as less than 35 mJ/m2. Bonding low energy surfaces by surface pre-treatments such as flame treatments, plasma treatments, oxidation, sputter etching, corona discharge, or primer treatments with a high surface energy material is well known. Such treatments disrupt the bonds at the surface of the low energy material providing sites which are reactive and which can participate in bonding reactions with adhesive materials. However, such surface pre-treatments are usually undesirable, in that they add cost to the process, they are not particularly reproducible in their results, and the effect of the pre-treatments wears off with time so the pre-treated surfaces must be re-pre-treated if they are not bonded within a reasonable period of time.
[0003] The chemistry of organic boron compounds has been studied in detail [see e.g. D. Barton and W. D. 011iis, "Comprehensive Organic Chemistry", Vol. 3, Part 14, Pergamon Press (1979) and H. C. Brown, Boranes in Organic Chemistry, Cornell University Press, Ithaca, N.Y. (1972)]. The use of organoboranes such as trialkylboranes including triethylborane and tributylborane for initiating and catalyzing the polymerization of vinyl monomers is well known. However, such organoborane compounds are known to be flammable in air so that the compounds and compositions containing them require special handling and the compositions have poor shelf stability [see e.g. U.S. Patent No. 3,236,823 (Jennes), and the Background section of U.S. Patent No. 5,935,711 (Pocius), at col. 2].
[0004] Certain alkylborane compounds and their use as initiators of polymerization are described in U.S. Patent Nos. 4,515,724, 4,638,092, 4,638,498, 4,676,858 and 4,921,921, each to Ritter.
[0005] U.S. Patent Nos. 5,106,928, 5,143,884, 5,286,821, 5,310,835 and 5,376,746, each disclose a two-part initiator system for acrylic adhesive compositions, in which the first part includes a reportedly stable organoborane amine complex and the second part includes a destabilizer or activator such as an organic acid or an aldehyde.
[0006] Japanese Patent Publication No. 548-18928 describes a method for adhering polyolefin or vinyl polymers using an adhesive obtained by adding trialkylboron to a vinyl monomer, with or without vinyl polymer. Examples of trialkylboron include triisopropylboron, tri-n-butylboron, tripropylboron and tri-tertbutylboron.
[0007] U.S. Patent No. 3,275,611 (Mottus) describes a process for polymerizing unsaturated monomers with a catalyst comprising an organoboron compound, a peroxygen compound and an amine complexing agent for the boron compound.
[0008] It is well known that the bonding of polyolefin substrates and other low surface energy substrates causes particular difficulties. Attempts have been made to overcome these difficulties by the extensive and expensive substrate surface preparation described above, or by priming the surface with a high surface energy primer. However, it is desired to develop adhesive compositions, which will bond low surface energy substrates without such surface preparation.
[0009] U.S. Patent No. 5,539,070 (Zharov), and U.S. Patent Nos. 5,616,796, 5,621,143, 5,681,910, 5,684,102, 5,686,544, 5,718,977, 5,795,657 and the '711 patent describe organoborane amine complexes which can be used in systems that initiate the polymerization of acrylic monomers in compositions useful for bonding low surface energy plastics substrates such as polyethylene, polypropylene and polytetrafluoroethylene.
[0010] International Patent Publication No. WO 01/4431 1 also describes amine organoborane complex polymerization initiators in bonding compositions for low surface energy substrates.
[0011] Tetraorganylborate salts of tetraalkylammonium, sodium or lithium are known as photoinitiators in photocurable compositions for imaging materials (see e.g. U.S. Patent Nos. 4,950,581, 6,10,987 and 6,171,700). Tetraorganylborate salts do not however have a boron-hydrogen bond. The distinction between boron-hydrogen compounds, triorganylboranes and organoborate salts is well illustrated in D. Barton and W. D. 01lis, "Comprehensive Organic Chemistry", to which Chapters 14.2, 14.3 and 14.4 of Vol. 3 are devoted.
[0012] More recently, Locfite (R&D) Ltd. has designed and developed technology that is described in International Patent Publication Nos. WO 02/34851, WO 02/34582 and WO 2003/089536 relating generally to polymerizable adhesive compositions with a free radically polymerizable component and an initiator system of an alkyl borohydride with either a metal or ammonium cation. These compositions also describe the use of aziridine components.
[0013] Henkel Corporation together with Loctite (R&D) Ltd. have designed and developed technology, which include a carrier to such polymerizable adhesive compositions so that the compositions have a flash point above 140 °F. See International Patent Publication No. WO 03/035703.
[0014] The use of aziridines generally however are under regulatory scrutiny, and thus labelling requirements are imposed, which may be an impediment to wide spread usage.
[0015] U.S. Patent Publication No. 2008/0090981 is directed to and claims the use of chlorosulfonated polyolefins and/or chlorinated polyolefins in combination with organosulfonyl halides in two-part organoborane:amine cured polymerisable compositions which accelerate cure speeds. However, non-chlorinated polyethylene and other common copolymers used as tougheners are not disclosed for use with organosulfonyl halides.
[0016] Despite the work of many in this general field of bonding low energy surfaces, there is a need for polymerizable compositions for bonding low surface energy substrates, such as polyolefins, and for end users to have a variety of such compositions which achieve that result through different technical strategies.
SUMMARY
[0017] In one aspect, the present invention provides a one-part photocurable composition comprising: (a) a (meth)acrylate component, (b) a Norrish type II photoinifiator; and (c) an borane-amine component.
[0018] Suitably, borane-amine component is an organoborane.
[0019] The borane-amine component may be present in an amount of from about 1 wt% to about 15 wt% based on the total weight of the composition. For example an organoborane-amine component may be present in an amount of from about 1 wt% to about 15 wt% based on the total weight of the composition.
[0020] The borane-amine component may comprise a borane of the formula: where independently each R is a hydrogen, a C1-C12 aliphatic, a C5-C20 aromatic group, or two or more of R may combine to form a ring structure.
[0021] Suitably, the borane-amine component comprises an organoborane of the formula: R \-B/R where independently each R is a Ci-C12 aliphatic, a Cs-C20 aromatic group, or two or more of R may combine to form a ring structure, where each R is optionally substituted with one or more of C1-C3 alkyl or C-C3 alkoxy, and where each R is optionally substituted with one or more hetereoatoms selected from S, N, 0 and P. Suitably, each R is optionally substituted with one or more heteroatoms selected from S or 0.
[0022] For example, each R may independently be a Ci-C12 alkyl or Ci-C12 alkoxy optionally substituted with one or more heteroatoms selected from S, N, 0 and P. [0023] The borane-amine component may comprise an organoborane such as a trialkyl organoborane.
[0024] The borane-amine component may comprises an amine of the formula: R1 R1 R1 where independently each R1 is hydrogen, a Ci-C12 aliphatic, a C5-C20 aromatic group, or two or more of R1 may combine to form a ring structure.
[0025] For example, each IR' may be a Ci-C12 alkyl or Ci-C12 alkoxy optionally substituted with one or more heteroatoms selected from S, N, 0 and P. [0026] Suitably, the borane-amine component is an organoborane-amine component and is selected from triethylborane-1,3-diaminopropane, tributylborane-3-methoxypropylamine, and triethylborane diethylenetriamine.
[0027] The methacrylate component may be a (meth)acrylate monomer having the formula: H2C=CGCO2R1, where G may be hydrogen, halogen or alkyl groups having from 1 to about 4 carbon atoms, and R1 may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups having from 1 to about 16 carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, polyurethane, carbonate, amine, amide, sulfur, sulfonate, and sulfone.
[0028] Suitably, the type II photoinifiator is selected from benzophenone, chlorobenzophenone, methyl-benzophenone, dimethylamino benzopheone, 4,4'-bis(dimethylamino)benzophenone, 5-dibenzosuberenone, xanthone, benzil, anthraquinone, 2-(hydroxymethyl)anthraquinone, 2-methylanthraquinone, and coumarin.
[0029] The one-part photocurable composition may further comprise a toughener. The toughener may for example be selected from styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS), styrene-isobutylene styrene (SIBS), styrene-bethylene/butylene-b-styrene (SE BS), and/or styrene-b-ethylene/propylene-b-styrene (SEPS). The toughener may be present in an amount of from about 1 wt% to about 20 wt% based on the total weight of the composition.
[0030] In one aspect, the one-part photocurable composition comprises: (a) a (meth)acrylate component; (b) a Norrish type II photoinitiator and (c) a borane-amine component; wherein the borane-amine component is an orgnoborane-amine component and is present in an amount of from about 2 wt% to about 8 wt% based on the total weight of the composition; wherein the orgnoborane-amine component comprises a trialkyl borane and an amine of the formula: where independently each R1 is hydrogen, a C1-C12 aliphatic, a C5-C20 aromatic group, or two or more of R1 may combine to form a ring structure; and wherein the type II photoinitiator is selected from the group consisting of benzophenone, chlorobenzophenone, methyl-benzophenone, dimethylamino benzopheone, 4,4'-bis(dimethylamino)benzophenone, 5-dibenzosuberenone, xanthone, benzil, anthraquinone, 2-(hydroxymethyl)anthraquinone, 2-methylanthraquinone, and coumarin.
[0031] Also provided herein is a method of bonding together two substrates comprising the steps of applying the photocurable one-part composition according to any preceding claim to at least one of the substrates, mating together the substrates and exposing the photocurable composition to radiation in the electromagnetic spectrum having a wavelength in the range of from 200 nm to 700 nm (full UVNis range) more preferably 200 nm to 400 nm (UV range) for a time sufficient to effect cure of the composition. For example, the photocurable composition may be exposed to radiation in the electromagnetic spectrum having a wavelength in the range of from 200 nm to 700 nm, more preferably 200 nm to 400 nm from a light source which is within 1 metre thereof, for example within 30 cm thereof. The duration of the exposure may be from about 0.1 seconds to about 360 minutes, such as from about 0.5 seconds to about minutes, for example from about 0.5 seconds to about 30 minutes, including from about 1 second to about 15 minutes, suitably, for a time period of less than about 240 seconds.
[0032] Suitably, one or both substrates are plastic or glass substrates. For example one or both substrates may be a polyolefin, such as polypropylene, polyethylene, polybutylene, polyisoprene, polymethylpentene and copolymers thereof. Suitably, at least one of the substrates is transmissive to UV radiation. One or more of the substrates may be transparent.
[0033] Advantageously, the compositions of the present invention are particularly useful for bonding low energy surfaces such as polyolefins.
DETAILED DESCRIPTION
(Meth)Acrylate Monomer Component [0034] The (meth)acrylate monomer component may comprise at least one (meth)acrylate ester selected from beta-carboxy ethyl acrylate, isobornyl acrylate, n- octyl acrylate, n-decyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, ethoxylated phenyl monoacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, n-butyl acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexane diol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylol propane diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, phenoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, glycerol mono-methacrylate, glycerol 1,3-dimethacrylate, trimethyl cyclohexyl methacrylate, methyl triglycol methacrylate, isobornyl methacrylate trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, hydroxybutyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, and poly(ethylene glycol) methacrylate.
[0035] Suitably, the (meth)acrylate monomer component comprises at least one (meth)acrylate component selected from isobornyl acrylate, tetrahydrofurfuryl acrylate, 2-carboxyethyl acrylate, di(ethylene glycol) ethyl ether acrylate and a diacrylate ester.
[0036] One or more suitable (meth)acrylates may be chosen from among polyfunctional (meth)acrylates, such as, but not limited to, di-or tri-functional (meth)acrylates like polyethylene glycol di(meth)acrylates, tetrahydrofuran (meth)acrylates and di(meth)acrylates, hydroxypropyl (meth)acrylate ("HPMA"), hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate ("TM PTMA"), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate ("TRIEGMA"), tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di- (pentamethylene glycol) dimethacrylate, tetraethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate and bisphenol-A mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate ("EBIPMA"), and bisphenol-F mono and di(meth)acrylates, such as ethoxylated bisphenol-F (meth)acrylate.
[0037] For example the anaerobically curable component may include Bisphenol A dimethacrylate: 0 [0038] Still other (meth)acrylates that may be suitable for use herein are silicone (meth)acrylate moieties ("SiMA"), such as those taught by and claimed in U.S. Patent No. 5,605,999 (Chu), the disclosure of which is hereby expressly incorporated herein by reference.
[0039] Other suitable materials may be chosen from polyacrylate esters represented by the formula: R40 [ o R4
I II II I
H2c=c-c-o -pc-0]-c-c=cul2 q where R4 is a radical selected from hydrogen, halogen or alkyl of from 1 to about 4 carbon atoms; q is an integer equal to at least 1, and preferably equal to from 1 to about 4; and X is an organic radical containing at least two carbon atoms and having a total bonding capacity of q plus 1. With regard to the upper limit for the number of carbon atoms in X, workable monomers exist at essentially any value. As a practical matter, however, a general upper limit is about 50 carbon atoms, such as desirably about 30, and desirably about 20.
[0040] For example, X can be an organic radical of the formula:
II II
where each of Y1 and Y2 is an organic radical, such as a hydrocarbon group, containing at least 2 carbon atoms, and desirably from 2 to about 10 carbon atoms, and Z is an organic radical, preferably a hydrocarbon group, containing at least 1 carbon atom, and preferably from 2 to about 10 carbon atoms. Other materials may be chosen from the reaction products of di-or tri-alkylolamines (e.g., ethanolamines or propanolamines) with acrylic acids, such as are disclosed in French Pat. No. 1,581,361.
[0041] Suitable oligomers with (meth)acrylate functionality may also be used.
Examples of such (meth)acrylate-functionalized oligomers include those having the following general formula: 0 -,R5 R5' (EV\ 0 if 1 I I I H2C=C-C-0 C I CI I C 0 C-C----CH2 R4 Rs 1:i" p R- _R4 where R5 represents a radical selected from hydrogen, alkyl of from 1 to about 4 carbon atoms, hydroxy alkyl of from 1 to about 4 carbon atoms, or
II
-a12-0-C-or-c(42 it4 I() where R4 is a radical selected from hydrogen, halogen, or alkyl of from 1 to about 4 carbon atoms; R6 is a radical selected from hydrogen, hydroxyl, or
II
-o-c-c=cH2 its m is an integer equal to at least 1, e.g., from 1 to about 15 or higher, and desirably from is 1 to about 8; n is an integer equal to at least 1, e.g., 1 to about 40 or more, and desirably between about 2 and about 10 and p is 0 or 1.
[0042] Typical examples of acrylic ester oligomers corresponding to the above general formula include di-, tri-and tetraethyleneglycol dimethacrylate; di(pentamethyleneglycol)dimethacrylate; tetraethyleneglycol diacrylate; tetraethyleneglycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; butyleneglycol dimethacrylate; neopentylglycol diacrylate; and trimethylolpropane triacrylate.
[0043] While di-and other polyacrylate esters, and particularly the polyacrylate esters described in the preceding paragraphs, can be desirable, monofunctional acrylate esters (esters containing one acrylate group) also may be used.
[0044] Suitable compounds can be chosen from among are cyclohexylmethacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethylacrylate, and chloroethyl methacrylate.
[0045] Another useful class of materials are the reaction product of (meth)acrylate-funcfionalized, hydroxyl-or amino-containing materials and polyisocyanate in suitable proportions so as to convert all of the isocyanate groups to urethane or ureido groups, respectively.
[0046] The so-formed (meth)acrylate urethane or urea esters may contain hydroxy or amino functional groups on the non-acrylate portion thereof. (Meth)acrylate esters suitable for use may be chosen from among those of the formula It 0 1-12C=C-C-0-1P-X-H where X is selected from -0--and
BY
where R9 is selected from hydrogen or lower alkyl of 1 through 7 carbon atoms; 57 is selected from hydrogen, halogen (such as chlorine) or alkyl (such as methyl and ethyl radicals); and R8 is a divalent organic radical selected from alkylene of 1 through 8 carbon atoms, phenylene and naphthylene.
[0047] These groups upon proper reaction with a polyisocyanate, yield a monomer of the following general formula: R70 I ft II H7CCCORX -c--NH where n is an integer from 2 to about 6; B is a polyvalent organic radical selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, alkaryl and heterocyclic radicals both substituted and unsubstituted, and combinations thereof; and R7, R8 and X have the meanings given above.
[0048] Depending on the nature of B, these (meth)acrylate esters with urea or urethane linkages may have molecular weights placing them in the oligomer class (such as about 1,000 g/mol up to about 5,000 g/mol) or in the polymer class (such as about greater than 5,000 g/mol).
[0049] Other unsaturated reactive monomers and oligomers such as styrenes, maleimides, vinyl ethers, allyls, allyl ethers and those mentioned in US6844080B1 (Kneafsey et al.) can be used. Vinyl resins as mentioned in US6433091 (Xia) can also be used. Methacrylate or acrylate monomers containing these unsaturated reactive groups can also be used.
[0050] Of course, combinations of these (meth)acrylates and other monomers may also be used.
[0051] Desirably the anaerobically curable component comprises at least one acrylate or methacrylate ester group.
[0052] Desirably the anaerobically curable component comprises is chosen from at least one of epoxy (meth)acrylates, urethane (meth)acrylates, urethane 20 di(meth)acrylates, alkyl (meth)acrylates, stearyl (meth)acrylates, isocyanurate (meth)acrylates, bisphenol-A-(meth)acrylates, ethoxylated bisphenol-A-(meth)acrylates, bisphenol-F-(meth)acrylates, ethoxylated bisphenol-F-(meth)acrylates, bisphenol-A di(meth)acrylates, ethoxylated bisphenol-A-di(meth)acrylates, bisphenol-F-di(meth)acrylates, and ethoxylated bisphenol-F-di(meth)acrylates.
[0053] The (meth)acrylate monomer component may be present in an amount of from about 10 wt% to about 80 wt% based on the total amount of photocurable compostion, suitably, the (meth)acrylate monomer component is present in an amount of from about 20 wt% to about about 55 wt%, desirably from about 25 wt% to about 50 wt%, such as from about 30 wt% to about 45 wt% based on the total weight of photocurable acrylate composition.
Borane-amine component [0054] The borane-amine component may be present in an amount of from about 1 wt% to about 15 wt% based on the total weight of the composition. For example, the borane-amine component may be present in an amount of from about 2 wt% to about 8 wt%, such as from about 3 wt% to about 6 wt% based on the total weight of the composition. Suitably, the borane-amine component is an organoborane-amine component which is present in an amount of from about 2 wt% to about 8 wt%.
[0055] As outlined above, the borane-amine component may comprise an organoborane of the formula:
R
where independently each R is a C1-C12 aliphatic, a C5-C20 aromatic group, or two or more of R may combine to form a ring structure, and where each R is optionally substituted with one or more heteroatoms selected from S, N, 0 and P. [0056] Suitably, R may be C1-C12 alkyl. For example, each R may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof.
[0057] The borane-amine component may comprise an amine of the formula: where independently each R1 is hydrogen, a Ci-C12 aliphatic, a C5-C20 aromatic group, or two or more of R1 may combine to form a ring structure.
[0058] Suitably, one or more or each R1 is a Ci-C12 alkyl optionally substituted with a Cl-C6 alkyl or a Cl-C6 alkoxy. For example each R1 may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof.
[0059] The borane-amine component may be an organoborane amine complex of the formula
R-B -H
where each R is Ci-C10 alkyl or phenyl, each R may optionally be substituted with one or more C1-C3 alkyl or C1-C6 alkoxy, and each R may optionally be substituted with one or more heteroatoms selected from 0, S and N, each R1 is hydrogen, or Ci-C10 alkyl which may optionally be substituted with one or more C1-C3 alkyl or C1-C6 alkoxy, or each R1 may be II2 (CH237: R2 in or N where each R2 is hydrogen or Ci-Ci0 alkyl, m is 2 to 10 and n is 1 to 6.
[0060] The alkyl groups mentioned throughout may be straight chained or branch chained.
[0061] Suitably, the R1 or R2 groups will be hydrogen or Ci-C4 alkyl, m will be 2 or 3 and n will be 1 or 2.
[0062] For example, the amine of the borane-amine component may be propylamine, dipropylamine, 2-methoxypropylamine, 3-methoxypropylamine, 1,3-diaminopropane, ethylamine, diethylamine, 2-methoxyethylamine, butylamine, dibutylamine, 4-methoxybutylamine, n-octylamine, 1,6-diaminohexane, diethylenetriamine, dipropylene diamine, ammonia, and 1,2-diaminopropane.
[0063] Preferred borane-amine components include tri-n-butylborane-3-methoxypropylamine complex, triethylborane-1,3-diaminopropane complex or combinations thereof.
[0064] Suitably, the borane-amine component may comprise an organoborane selected from tri-n-octylborane, tridodecylborane, triethylborane, tri-n-butylborane and tri-secbutylborane; and the amine component may be selected from 1,3-propanediamine, 1,6-hexanediamine, methoxypropylamine, diethylenetriamine, isophorone diamine, aminomethyltrimethoxysilane, 3-aminopropyl trimethoxysilane, aminomethyltriethoxysilane, 3-aminopropyltriethoxysilane, 2- (trimethoxysilylethyl)pyridine, aminopropylsilanetriol, 3-(m-aminophenoxy)propyltrimethoxysilane, 3-aminopropyldiisopropylmethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltris(methoxy ethoxy)silane, N-(2- aminoethyl)aminomethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(6-aminohexyl)aminomethyltrimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane.
Photoinitiator [0065] A free radical photoinitiator initiates the polymerization of monomers when exposed to actinic radiation by the formation of a free radical. Photoinitiators are frequently used in UV-curable compositions, such as in photocurable adhesives or in UV-curable inkjet inks.
[0066] Two types of free radical photoinitiators can be distinguished. A Norrish Type I initiator is an initiator which cleaves after excitation, yielding the initiating radical immediately. A Norrish Type II-initiator is a photoinitiator which is activated by actinic radiation and forms free radicals by hydrogen abstraction from a second compound that becomes the actual initiating free radical. This second compound is called a co-initiator or polymerization synergist.
[0067] Examples of suitable Norrish Type II photoinitiators are aromatic ketones such as benzophenone, xanthone, derivatives of benzophenone (e.g. chlorobenzophenone), blends of benzophenone and benzophenone derivatives (e.g. Photocure 81, a 50/50 blend of 4-methyl-benzophenone and benzophenone), Michler's Ketone, Ethyl Michler's Ketone, thioxanthone and other xanthone derivatives like Quantacure ITX (isopropyl thioxanthone), 5-dibenzosuberenone, benzil, anthraquinones (e.g. 2-ethyl anthraquinone), coumarin, and the like. Chemical derivatives and combinations thereof may also be used.
[0068] The Norrish Type II photoinitiator may be present in an amount of from 1 wt% to about 40 wt% based on the total weight of the one-part photocurable acrylate 5 composition.
[0069] Suitably, the photoinitiator is present in an amount of from about 10 wt% to about 25 wt% based on the total weight of the composition.
Toughener [0070] Some embodiments of the present invention may comprise a toughener component. Examples of toughener components include synthetic rubbers, such as acrylonitrile/butadiene rubber (NBR rubber), a polyurethane, styrene/butadiene rubber, styrene/butadiene/methacrylate rubber, chloroprene rubber or butadiene rubber, a natural rubber, a styrene thermoplastic elastomer such as styrene/polybutadiene/styrene synthetic rubber, a polyacrylate or polymethacrylate elastomer, a methacrylate/acrylate block co-polymer or an olefin thermoplastic elastomer such as polystyrene/EPDM (an ethylene/propylene/conjugated diene copolymer) synthetic rubber. Chlorinated and chlorosulfonated polyethylene elastomers can also be used. The toughener component can also be a mixture or dispersion of these types of materials.
[0071] The toughener component can be present in an amount from about 5 to about 50% weight percentage based on the total weight of the composition, desirably in an amount from about 10 to about 30% weight percentage based on the total weight of the composition
Examples
[0072] The photocurable acrylate composition may have the following components, said components may be mixed together to form the photocurable acrylate composition: Photocurable (meth)acrylate composition Component Amount (wt%) (meth)acrylate monomer 40-98 Organoborane-amine component 1-15 Type II photoinifiator 1-50
EXAMPLE 1
[0073] The following formulation was prepared: Component Amount (wt%) Tetrahydrofurfuryl methacrylate 29.2 (hydroxyethyOmethacrylate 16.7 Treithylborane-1,3-diaminopropane complex 4.2 Benzophenone 8.3 Methyl methacrylate 30.4 Tuftec H1517 11.3 [0074] The composition of example 1 was employed to bond the following substrates, and load at bond failure strengths are also specified: Substrate 1 Substrate 2 Load at Failure (M Pa) Type of Failure Polypropylene Polypropylene 1.2 Adhesive High density High density 1.4 Adhesive polyethylene polyethylene Polypropylene Glass 2.4 Adhesive failure to glass and cohesive failure of the adhesive layer (mixed) High density Glass 1.5 Adhesive failure to glass and adhesive polyethylene failure to high density polyethylene [0075] The composition of example 1 was applied to an end region of a lap shear having the following dimensions 2.54 cm X 10.16 cm X 0.3 cm (width X length X thickness), the composition was applied as a drop or a globule onto the centre of the end region of the lap shear; a second lap shear was mated with the first lap shear to form an overlap joint of length 1.27 cm said overlap joint having an area of 3.23 cm2. When the two lap shears were mated the drop or globule of adhesive was squeezes in the overlapping area creating a thin layer of adhesive between the lap shear specimen. The composition was exposed to UV radiation, through the lap shear, from a 375 nm LED light source at 900 mW/cm2 for 60 seconds to cure the adhesive. Bonding was carried out at room temperature. The bonded specimens were tested 1 day after curing of the adhesive joints. To test the bonded specimen were placed in the grips of a calibrated Hounsfield tensile testing machine and pulled to failure at a rate of 2 mm per minute.
[0076] All testing was carried out in accordance with ASTM D3163: Strength properties of adhesively bonded rigid plastic lap-shear joints in shear by tension loading and in accordance with ISO 4587: Adhesives -determination of tensile lap shear strength of high strength adhesive bonds.
EXAMPLE 2
[0077] The following formulation was prepared: Component Amount (wt%) Tetrahydrofurfuryl methacrylate 44.1 Tributylborane 3-methoxypropyl amine 5.9 complex Benzophenone 11.8 Methyl methacrylate 27.9 Tuftec H1517 10.3 [0078] The composition of example 2 employed to bond the following substrates, and load at bond failure strengths are also specified: Substrate 1 Substrate 2 Load at Failure (M Pa) Type of Failure Polypropylene Polypropylene 1.5 Adhesive Polypropylene Glass 3.5 50% adhesive failure to glass, 50% adhesive failure to polypropylene [0079] The composition of example 2 was tested in the same manner as outlined above for example 1.
EXAMPLE 3
[0080] The following formulation was prepared: Component Amount (wt%) Tetrahydrofurfuryl methacrylate 40.3 Triethylborane - 1,3-diaminopropane 5.4 complex 5-dibenzosuberenone 19.4 Methyl methacrylate 25.5 Tuftec H1517 9.4 [0081] The composition of example 3 was employed to bond the following substrates, and load at load at bond failure strengths are also specified: Substrate 1 Substrate 2 Load at Failure (MPa) Type of Failure Polypropylene Polypropylene 1.5 Adhesive Polypropylene Glass 3.5 50% adhesive failure to glass, 50% adhesive failure to polypropylene [0082] The composition of example 3 was tested in the same manner as outlined above for example 1.
EXAMPLE 4
[0083] The following formulation was prepared: Component Amount (wt%) Tetrahydrofurfuryl methacrylate 43.5 Tributylborane - 3-methoxypropylamine 5.8 complex 5-dibenzosuberenone 13.0 Methyl methacrylate 27.5 Tuftec H1517 10.1 [0084] The composition of example 3 was employed to bond the following substrates, and load at load at bond failure strengths are also specified: Substrate 1 Substrate 2 Load at Failure (M Pa) Type of Failure Polypropylene Glass 2.55 50% adhesive failure to glass 50% adhesive failure to polypropylene High density Glass 2.14 75% adhesive polyethylene failure to glass, 25% adhesive failure to high density polyethylene [0085] The composition of example 3 was tested in the same manner as outlined above for example 1.
COMPARATIVE EXAMPLE
[0086] The following formulation was prepared: Component Amount (wt%) Tetrahydrofurfuryl methacrylate 45.2 3-methoxypropylamine 2.0 5-dibenzosuberenone 13.6 Methyl methacrylate 28.7 Tuftec H1517 10.6 [0087] The composition of the comparative example was employed to bond the following substrates, and load at load at bond failure strengths are also specified: Substrate 1 Substrate 2 Load at Failure Type of Failure (MPa) Polypropylene Glass 0.1 adhesive failure to polypropylene [0088] The composition of the comparative example was tested in the same manner as outlined above for example 1. The comparative example does not comprise an organoborane-amine component and cannot effect bonding between polypropylene and glass.
[0089] Advantageously, when the photocurable composition of the present invention is exposed to radiation in the electromagnetic spectrum having a wavelength in the range of from 200 nm to 700 nm, the absorption of such radiation by a type II photoinifiator leads to the generation of an excited electron state in the photointiator ft) that will react with the borane-amine component by abstracting a hydrogen from the amine component, which in turn leads to the release of the borane component (i.e. decomplexation of the borane from the borane-amine component). The borane component can then oxidise leading to the generation of highly reactive radical species which can abstract a hydrogen from low energy surfaces such as a polyolefin surface.
The resulting radical species on the low energy surface can react with the (meth)acrylate leading to grafting of polymerised (meth)acrylate with the low energy surface.
[0090] In contrast, Norrish type I photoinifiators would lead to polymerisation of the (meth)acrylate monomer, without grafting to a low energy surface occurring.
[0091] While (meth)acrylate compositions comprising borohydride species have demonstrated utility in bonding low energy surfaces in two-part compositions, borohydride species have not been successfully employed to form one-part (meth)acrylate adhesive compositions.
[0092] Advantageously, the compositions of the present invention are particularly useful for bonding two or more substrates, wherein at least one of said substrates is a polyolefin substrate.
[0093] The words "comprises/comprising" and the words "having/including" when used herein with reference to the present invention are used to specify the presence of stated features, integers, steps or components but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
[0094] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
Claims (18)
- Claims 1) A one-part photocurable composition comprising: (a) a (meth)acrylate component; (b) a Norrish type II photoinifiator; and (c) a borane-amine component.
- 2) The one-part photocurable composition according to claim 1, wherein the borane-amine component is present in an amount of from about 1 wt% to about 15 wt% based on the total weight of the composition.
- 3) The one-part photocurable composition according to claim 1 or claim 2, wherein the borane-amine component comprises an organoborane-amine component.
- 4) The one-part photocurable composition according to any preceding claim, wherein the borane-amine component comprises an organoborane of the formula:R Rwhere independently each R is a Ci-C12 aliphatic, a C5-C20 aromatic group, or two or more of R may combine to form a ring structure, where each R is optionally substituted with one or more of C1-C3 alkyl or C1-C3 alkoxy and where each R is optionally substituted with one or more heteroatoms selected from S, N, 0 and P.
- 5) The one-part photocurable composition according to claim 4, wherein independently each R is a Ci-C12 alkyl or Ci-C12 alkoxy optionally substituted with one or more heteroatoms selected from S, N, 0 and P.
- 6) The one-part photocurable composition according to claim 3 to 5, wherein the organoborane is a trialkyl borane.
- 7) The one-part photocurable composition according to any preceding claim wherein the borane-amine component comprises an amine of the formula: where independently each R1 is hydrogen, a C1-C12 aliphatic, a C5-C20 aromatic group, or two or more of R1 may combine to form a ring structure.
- 8) The one-part photocurable composition according to claim 7, wherein each R1 is a Ci-C12 alkyl or Ci-C12 alkoxy optionally substituted with one or more heteroatoms selected from S, N, 0 and P.
- 9) The one-part photocurable composition according to any preceding claim, wherein the borane-amine component is selected from the group consisting of triethylborane-1,3-diaminopropane, tributylborane-3-methoxypropylamine, and triethylborane diethylenetriamine.
- 10) The one-part photocurable composition according to any preceding claim, wherein the methacrylate component comprises a (meth)acrylate monomer having the formula: H2C=CGCO2R1, wherein G may be hydrogen, halogen or alkyl groups having from 1 to about 4 carbon atoms, and R1 may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups having from 1 to about 16 carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, polyurethane, carbonate, amine, amide, sulfur, sulfonate, and sulfone.
- 11) The one-part photocurable composition according to any preceding claim, wherein the type II photoinitiator is selected from the group consisting of benzophenone, chlorobenzophenone, methyl-benzophenone, dimethylamino benzopheone, 4,4'-bis(dimethylamino)benzophenone, 5-dibenzosuberenone, xanthone, benzil, anthraquinone, 2-(hydroxymethyl)anthraquinone, 2-methylanthraquinone, and coumarin.
- 12) The one-part photocurable composition according to any preceding claim, further comprising a toughener.
- 13) The one-part photocurable composition according to claim 12, wherein the toughener is selected from the group consisting of styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS), styrene-isobutylene styrene (SIBS), styrene-bethylene/butylene-b-styrene (SE BS), and/or styrene-b-ethylene/propylene-b-styrene (SEPS).
- 14) The one-part photocurable composition according to claim 12 or 13, wherein the toughener is present in an amount of from about 1 wt% to about 20 wt% based on the total weight of the composition.
- 15) A one-part photocurable composition comprising: (a) a (meth)acrylate component; (b) a Norrish type II photoinifiator and (c) a borane-amine component; wherein the borane-amine component is an orgnoborane-amine component and is present in an amount of from about 2 wt% to about 8 wt% based on the total weight of the composition; wherein the orgnoborane-amine component comprises a trialkyl borane and an amine of the formula: where independently each R1 is hydrogen, a C1-C12 aliphatic, a C5-C20 aromatic group, or two or more of R1 may combine to form a ring structure; and wherein the type II photoinitiator is selected from the group consisting of benzophenone, chlorobenzophenone, methyl-benzophenone, dimethylamino benzopheone, 4,4'-bis(dimethylamino)benzophenone, 5-dibenzosuberenone, xanthone, benzil, anthraquinone, 2-(hydroxymethyl)anthraquinone, 2-methylanthraquinone, and coumarin.
- 16) A method of bonding together two substrates comprising the steps of applying the photocurable one-part composition according to any preceding claim to at least one of the substrates, mating together the substrates and exposing the photocurable composition to radiation in the electromagnetic spectrum having a wavelength in the range of from 200 nm to 700 nm (full UV/Vis range) more preferably 200 nm to 400 nm (UV range) for a time sufficient to effect cure of the composition.
- 17) The method of bonding together two substrates according to claim 16, wherein one or both substrates are plastic or glass substrates.
- 18) The method of bonding together two substrates according to claim 16 or 17, wherein one or both substrates are polyolefins e.g. polypropylene, polyethylene, polybutylene, polyisoprene, polymethylpentene and copolymers thereof.TOMKINS & CO
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| GB1821125.0A GB2580162B (en) | 2018-12-21 | 2018-12-21 | One-part photocurable (meth) acrylate compositions |
| PCT/EP2019/083340 WO2020126442A1 (en) | 2018-12-21 | 2019-12-02 | One-part photocurable (meth) acrylate compositions |
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| GB1821125.0A GB2580162B (en) | 2018-12-21 | 2018-12-21 | One-part photocurable (meth) acrylate compositions |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11866609B2 (en) * | 2017-12-13 | 2024-01-09 | 3M Innovative Properties Company | Optically clear adhesives containing a trialkyl borane complex initiator and photoacid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5690780A (en) * | 1995-02-22 | 1997-11-25 | Minnesota Mining And Manufacturing Company | Polymerizable compositions made with polymerization initiator systems based on organoborane amine complexes |
| US20060235101A1 (en) * | 2002-06-06 | 2006-10-19 | Messe Laurence J | Actinic radiation curable compositions and their use |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE599646A (en) | 1960-02-02 | |||
| US3275611A (en) | 1960-12-30 | 1966-09-27 | Monsanto Co | Process for polymerizing unsaturated monomers with a catalyst comprising an organoboron compound, a peroxygen compound and an amine |
| DE1719144C3 (en) | 1967-12-01 | 1974-08-22 | Henkel & Cie Gmbh, 4000 Duesseldorf | Accelerated hardening adhesives or sealants in the absence of oxygen |
| JPS4818928B1 (en) | 1969-12-13 | 1973-06-09 | ||
| US4638498A (en) | 1980-06-20 | 1987-01-20 | Rca Corporation | Digital timing system |
| DE3207263A1 (en) | 1982-03-01 | 1983-09-08 | Henkel KGaA, 4000 Düsseldorf | SUBSTANCE MIXTURES CONTAINING ORGANO BORON COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3201780A1 (en) | 1982-01-21 | 1983-08-25 | Henkel KGaA, 4000 Düsseldorf | NEW POLYMERS ORGANO BORON COMPOUNDS AND THEIR USE |
| DE3207264A1 (en) | 1982-03-01 | 1983-09-08 | Henkel KGaA, 4000 Düsseldorf | NEW BORALKYL COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3518965A1 (en) | 1985-05-25 | 1986-11-27 | Henkel KGaA, 40589 Düsseldorf | Plastic compositions which can be melted and at the same time cure aerobically, and process for their preparation |
| JPS6312616A (en) * | 1986-07-02 | 1988-01-20 | Nippon Foil Mfg Co Ltd | Photosensitive resin composition |
| US4950581A (en) | 1987-07-06 | 1990-08-21 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
| US5106928A (en) | 1991-04-29 | 1992-04-21 | National Starch And Chemical Investment Holding Corporation | Acrylic adhesive composition and organoboron initiator system |
| US5143884A (en) | 1991-04-29 | 1992-09-01 | National Starch And Chemical Investment Holding Corporation | Acrylic adhesive composition and organoboron initiator system |
| US5286821A (en) | 1992-03-17 | 1994-02-15 | National Starch And Chemical Investment Holding Corporation | Acrylic adhesive composition and organoboron initiator system |
| US5310835A (en) | 1993-09-30 | 1994-05-10 | National Starch And Chemical Investment Holding Corporation | Transparent two-part acrylic adhesive composition and the method of use thereof |
| EP1029906B1 (en) * | 1994-02-22 | 2004-12-08 | Minnesota Mining And Manufacturing Company | Bonded composite containing polymerisable acrylic composition made with polymerisation initiator systems based on organoborane amine complexes |
| EP0746573B1 (en) | 1994-02-22 | 2001-06-06 | Minnesota Mining And Manufacturing Company | Polymerizable compositions made with polymerization initiator systems based on organoborane amine complexes |
| US5616796A (en) | 1995-04-14 | 1997-04-01 | Minnesota Mining And Manufacturing Company | Organoborane polyamine complexes and adhesive composition made therewith |
| US5621143A (en) | 1995-04-14 | 1997-04-15 | Minnesota Mining And Manufacturing Company | Organoborane polyoxyalkylenepolyamine complexes and adhesive compositions made therewith |
| US5605999A (en) | 1995-06-05 | 1997-02-25 | Loctite Corporation | Anaerobically curable silicones |
| US5686544A (en) | 1995-08-11 | 1997-11-11 | Minnesota Mining And Manufacturing Company | Organoborane polyamine complex initiator systems and polymerizable compositions made therewith |
| JP3431782B2 (en) | 1996-03-08 | 2003-07-28 | 昭和高分子株式会社 | Curable composite material composition and curing method thereof |
| JPH1081838A (en) | 1996-07-16 | 1998-03-31 | Showa Denko Kk | Photocurable material and method for curing the same |
| US5935711A (en) | 1996-10-23 | 1999-08-10 | 3M Innovative Properties Company | Organoborane amine complex initiator systems and polymerizable compositions made therewith |
| US6806330B1 (en) | 1999-12-17 | 2004-10-19 | Dow Global Technologies Inc. | Amine organoborane complex polymerization initiators and polymerizable compositions |
| EP1328425B1 (en) | 2000-10-20 | 2005-06-15 | Continental Teves AG & Co. oHG | Shaft locking device |
| EP1201722A1 (en) | 2000-10-23 | 2002-05-02 | Loctite (R & D) Limited | Polymerisation initiators, polymerisable compositions, and uses thereof |
| US6433091B1 (en) | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
| WO2003035703A1 (en) | 2001-10-23 | 2003-05-01 | Henkel Corporation | Non-flammable and non-combustible adhesive bonding systems having adherence to low energy surfaces |
| WO2003089536A2 (en) | 2002-04-19 | 2003-10-30 | Loctite (R & D) Limited | Polymerisation initiators based on ammonium tetraalkyl boranes, polymerisable compositions, and uses thereof for bonding low surface energy substrates |
| US7524907B2 (en) | 2006-10-12 | 2009-04-28 | Dow Global Technologies, Inc. | Accelerated organoborane initiated polymerizable compositions |
| EP2834314A1 (en) * | 2012-04-06 | 2015-02-11 | Ips Corporation | Adhesive composition for bonding low surface energy polyolefin substrates |
-
2018
- 2018-12-21 GB GB1821125.0A patent/GB2580162B/en active Active
-
2019
- 2019-12-02 WO PCT/EP2019/083340 patent/WO2020126442A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5690780A (en) * | 1995-02-22 | 1997-11-25 | Minnesota Mining And Manufacturing Company | Polymerizable compositions made with polymerization initiator systems based on organoborane amine complexes |
| US20060235101A1 (en) * | 2002-06-06 | 2006-10-19 | Messe Laurence J | Actinic radiation curable compositions and their use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11866609B2 (en) * | 2017-12-13 | 2024-01-09 | 3M Innovative Properties Company | Optically clear adhesives containing a trialkyl borane complex initiator and photoacid |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201821125D0 (en) | 2019-02-06 |
| GB2580162B (en) | 2022-07-13 |
| WO2020126442A1 (en) | 2020-06-25 |
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