CN102203200A - 用于涂料、膜或粘合剂的包含膦酸酯的增粘剂 - Google Patents
用于涂料、膜或粘合剂的包含膦酸酯的增粘剂 Download PDFInfo
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- CN102203200A CN102203200A CN2009801431933A CN200980143193A CN102203200A CN 102203200 A CN102203200 A CN 102203200A CN 2009801431933 A CN2009801431933 A CN 2009801431933A CN 200980143193 A CN200980143193 A CN 200980143193A CN 102203200 A CN102203200 A CN 102203200A
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- Prior art keywords
- methyl
- branching
- alkyl
- acrylate
- composition
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 12
- 150000002148 esters Chemical class 0.000 title description 10
- 239000002318 adhesion promoter Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 53
- -1 acrylic ester Chemical class 0.000 claims description 69
- 238000000576 coating method Methods 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 44
- 125000001931 aliphatic group Chemical group 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000003673 urethanes Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- YOQPJXKVVLAWRU-UHFFFAOYSA-N ethyl carbamate;methyl prop-2-enoate Chemical compound CCOC(N)=O.COC(=O)C=C YOQPJXKVVLAWRU-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 230000001464 adherent effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 4
- 230000001737 promoting effect Effects 0.000 abstract 2
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 16
- 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 15
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 125000004386 diacrylate group Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 229940106691 bisphenol a Drugs 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 150000004646 arylidenes Chemical group 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- 150000003008 phosphonic acid esters Chemical class 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KYEAMYHCEZEPOJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylphosphonic acid Chemical class CC(=C)C(=O)OCCCP(O)(O)=O KYEAMYHCEZEPOJ-UHFFFAOYSA-N 0.000 description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- WGOQVOGFDLVJAW-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O WGOQVOGFDLVJAW-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 210000004268 dentin Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical class [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- MYYLFDRHMOSOJJ-UHFFFAOYSA-N (3-methylphenyl)-(4-phenylphenyl)methanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC(=CC=2)C=2C=CC=CC=2)=C1 MYYLFDRHMOSOJJ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- MYCQSOCJLZBPAT-UHFFFAOYSA-N 2-methylprop-2-enoic acid;potassium Chemical compound [K].CC(=C)C(O)=O MYCQSOCJLZBPAT-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- DEBAKWBAUARYEA-UHFFFAOYSA-N C1=CC=CC=C1C1=CC=CC=C1.CC1=CC(C)=C(C(=O)[PH2]=O)C(C)=C1 Chemical compound C1=CC=CC=C1C1=CC=CC=C1.CC1=CC(C)=C(C(=O)[PH2]=O)C(C)=C1 DEBAKWBAUARYEA-UHFFFAOYSA-N 0.000 description 1
- 0 CNC(C(c1ccc(**)cc1)=O)(N)ON Chemical compound CNC(C(c1ccc(**)cc1)=O)(N)ON 0.000 description 1
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- 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
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- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- 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
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract
本发明涉及在表面上的组合物如涂料、膜或粘合剂,其包含a)至少一种(甲基)丙烯酸酯预聚物,b)式(I)增粘单体,其中Q、R1、R2、R4、R5、m和n如本文中定义。另外,该组合物可用于改善对表面,尤其是金属表面的粘合且可包括其他任选组分如增粘光引发剂。
Description
本发明涉及(甲基)丙烯酸酯膦酸酯在各种预聚物体系中改善所形成的树脂对金属表面的粘合的用途。
含磷材料作为阻燃剂、腐蚀抑制剂、增粘剂和防垢剂的用途是已知的。常规含磷添加剂为不可聚合的且遭遇几个缺点,例如迁移和浸析,导致粘合剂、涂层或膜性能随时间改变。市售含磷单体,例如乙烯基膦酸和乙基膦酸单乙烯基酯显示出降低的聚合倾向并获得具有低分子量的聚合物。
市售含(甲基)丙烯酸官能的烷基磷酸酯显示出降低的水解稳定性,因为磷酸酯或甲基丙烯酸酯酯键可在水的存在下分解。这降低了它们的储存稳定性并限制它们的应用。
已知(甲基)丙烯酸膦酸和酯比类似的磷酸酯酸和酯更加水解稳定。也已知这些单体的阻燃剂和防垢活性。
例如,美国专利Nos.3,030,347和2,934,555教导了二烷基膦酰烷基丙烯酸酯和甲基丙烯酸酯共聚物和制备方法。所述化合物用于皮革或织物修饰中以赋予阻燃性。
美国专利No.4,526,728讨论了用于染色助剂和防垢剂的膦酸酯单体。
美国出版的申请2008/194730公开了含膦酸结构部分的自吸牙科粘合剂组合物。该发明宣称在搪瓷和/或牙质上粘结强度为至少8Mpa。
美国专利No.4,029,679公开了作为金属底漆的膦酸酯单体。
美国专利No.6,740,173公开了膦酸酯低聚物和膦酸酯单体(膦酸酯化甲基丙烯酸酯)在组合物中用于防止粘合剂和金属反应性添加剂对金属腐蚀。
Bressy-Brondino,C.等,Journal of Applied Polymer Science 2002,83(11),2277-2287公开了作为钢上的涂层的聚(偏二氟乙烯)和甲基丙烯酸甲酯与2-甲基丙烯酰氧基乙基膦酸二甲酯的共聚物的混合物。
美国专利No.6,436,475公开了一种处理锌、镁或铝的方法,其中将具有至少一个磷酸或膦酸基团的有机化合物施涂在金属表面上。
美国专利Nos.4,738,870和4,658,003公开了作为增粘单体的羟基氧膦基烷基(甲基)丙烯酸酯。
仍需要水解稳定的含磷单体,其可通过将含磷单体与至少一种固化剂和固化树脂简单混合而容易地掺入树脂基涂料、膜和粘合剂中。令人惊讶的是,更加水解稳定的膦酸酯基组合物也显示出对金属的优异粘合。
发明概述
本发明包括一种在表面上的涂料、膜或粘合剂,所述涂料、膜或粘合剂包含:
a)至少一种(甲基)丙烯酸酯预聚物,
b)式(I)增粘单体:
Q为至少一个选自一个或多个线性或支化C1-C10烷基、线性C1-C18亚烷基、C6-C12亚芳基或线性或支化亚芳烷基的二价连接基团;
其中线性或支化C1-C10烷基、C6-C12亚芳基、线性或支化亚芳烷基连接基团未被取代或被一个或多个C1-C4烷基、C1-C4卤代烷基、卤素、羟基或C1-C4烷氧基取代;
或
Q为被一个或多个-O-、-S-、-O(CO)-、-S(CO)-、-OC(O)O-或-C(O)-间隔的C2-C12亚烷基;
m为1-2;
n为1-2;
R1和R2独立地为氢或线性或支化C1-C4烷基;
R4和R5独立地为氢或线性或支化C1-C4烷基;
和
c)固化剂。
在式(I)中,Q必须经由碳原子直接连接在磷原子上。
(甲基)丙烯酸酯预聚物优选为含(甲基)丙烯酸酯官能的环氧树脂或脂族氨基甲酸酯或其混合物。环氧树脂还例如含有(甲基)丙烯酸酯结构部分。
R4和R5例如独立地为线性或支化C1-C4烷基或氢。例如,R4或R5为氢或R4或R5中至少一个为氢。
Q优选为C3-C18亚烷基。
例如,当预聚物为含(甲基)丙烯酸酯官能的脂族氨基甲酸酯时,Q为C3-C18亚烷基、C3-C12亚烷基、C3-C10亚烷基、C3-C8亚烷基或C3-C6亚烷基。
本发明还包括至少部分覆盖有由组分a)、b)和c)形成的固化涂料、膜或粘合剂的表面。至少部分覆盖的表面或基质优选排除牙质釉质。
表面优选为金属,例如铝或钢。表面紧邻涂层,所述涂层包含含有a)、b)和c)的涂料、膜或粘合剂。
此外,金属表面可以为刚性或挠性的。要求挠性表面的应用可以为卷材涂料。
卷材涂料包括将有机树脂施涂在平坦金属表面上。金属例如为铝或钢。在该方法中,金属盘管为未卷绕的,清洁的,处理的,涂底漆的,固化的,用面漆处理的,固化的和再卷绕的。当金属卷到达用户时,它未卷绕并塑造成最终产品。最终产品例如为屋顶或建筑物外观、办公家具、档案柜、电气用具或汽车的排气罩或门。当将它辊压以储存和运输,然后变平、切割、成型并固定时,置于卷材涂层上的危险应力要求涂层是耐久的。可在曝露在湿气、阳光和大气中各种化学品下的室外应用中的金属物体的寿命期间也要求耐久性。为透明或轻微染色的树脂的底漆层的优异粘合对最终产品的制造和使用寿命期间在金属上的涂料可接受性能是重要的。
式(I)所述的增粘单体用于改善涂料、膜或粘合剂的粘着性能。通过式(I)所述单体增粘可以以大量方法进行。例如,可将合适的表面用式(I)增粘单体处理,其后将可固化预聚物施涂在所述处理的表面上并固化。
作为选择,可将式(I)增粘单体在表面处理以前溶于溶剂中,其后将可固化预聚物施涂在所述处理的表面上并固化。
也可将式(I)增粘单体与预聚物结合,形成组合物,然后将其施涂在表面上并固化。
另一选择是可将式(I)增粘单体聚合形成预聚物或低聚物,然后将其直接加入含烯属不饱和的其它低聚物或树脂如(甲基)丙烯酸酯,以及增粘剂和光引发剂中。
因此,本发明还包括几种方法:
一种改善涂料、膜或粘合剂对表面的粘合的方法,所述方法包括以下步骤:
i)用上述式(I)增粘单体处理表面,
将包含(甲基)丙烯酸酯预聚物和固化剂的组合物施涂在所述处理的表面上;
或
将包含上述式(I)增粘单体、(甲基)丙烯酸酯预聚物和固化剂的组合物施涂在表面上;
或
使上述式(I)增粘单体聚合形成增粘低聚物,
将所述低聚物加入(甲基)丙烯酸酯预聚物中,
和
ii)固化。
固化剂优选为光引发剂。
发明详述
定义
就本发明而言,分子量意指重均分子量(Mw)。
就本发明而言,术语“单体”指能聚合的烯属不饱和化合物。
就本发明而言,术语“单体单元”指在聚合以后单体引入聚合物中。
除非另有说明,参考“百分数”基于组合物总重量的重量百分数。
就本发明而言,“预聚物”意指能进一步聚合的反应性低分子量大分子。
就本发明而言,“增粘低聚物”意指由式(I)单体形成的低聚物。该低聚物可包括其它单体,但优选仅由式(I)单体或(I)单体的混合物形成。
术语“低聚物”例如为聚合物分子,但是其仅由几个单体单元组成,例如二聚物、三聚物和四聚物。
(甲基)丙烯酸酯包括甲基丙烯酸酯和丙烯酸酯衍生物。
式(I)增粘单体:
Q为至少一个选自一个或多个线性或支化C1-C10烷基、线性C1-C18亚烷基、C6-C12亚芳基或线性或支化亚芳烷基的二价连接基团;
其中线性或支化C1-C10烷基、C6-C12亚芳基、线性或支化亚芳烷基连接基团未被取代或被一个或多个C1-C4烷基、C1-C4卤代烷基、卤素、羟基或C1-C4烷氧基取代;
或
Q为被一个或多个-O-、-S-、-O(CO)-、-S(CO)-、-OC(O)O-或-C(O)-间隔的C2-C12亚烷基;
m为1-2;
n为1-2;
R1和R2独立地为氢或线性或支化C1-C4烷基;
R4和R5独立地为氢或线性或支化C1-C4烷基;
C1-C18亚烷基为线性的,例如为C1-C4、C1-C6、C1-C8、C1-C10、C1-C12、C1-C14、C1-C16。
实例为亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基和亚十二烷基。其它实例为C1-C8亚烷基、C1-C6亚烷基或C2-C6亚烷基、C1-C4亚烷基或C2-C4亚烷基。
Q可例如为C3-C18。具体实例为-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-和-CH2CH2CH2CH2CH2CH2-。
Q可例如为线性或支化C1-C10烷基。例如-CH2CH(CH3)CH2-、(-CH2CH2)2C(CH2CH2-)2或-CH2CH2CH(CH2CH2-)2。
其中连接基团Q为支化的式(I)的实例如下。
Q可例如为二价、三价或四价的。
当n为1且m为1时,式(I’)为:
尽管不受理论约束,认为至少C3或较大亚烷基连接基团改善涂料、膜或粘合剂的粘合,这是由于它使得膦酸基团更容易地附着在金属表面上。长间隔基通过使它远离聚合物骨架并使它正确定位以与金属结合而赋予“锚”基团挠性。另外,较长的间隔基提高P-C连接键对水解的稳定性。
C1-C4烷氧基例如为甲氧基、乙氧基、丙氧基和丁氧基,烷氧基中的烷基可具有大于两个碳原子且可为支化的。
被一个或多个-O-、-S-、-O(CO)-、-S(CO)-、-OC(O)O-、-C(O)-O-或-C(O)-基团间隔的C2-C12亚烷基可例如被-O-间隔一次或几次。例如,它可被不连续的-O-间隔1-5次,例如1-3次或一次或两次。因此,所得结构单元例如为-CH2-O(CH2)2O-CH2-、-CH2-O-CH2-和-CH2CH2-O-CH2CH2-。
C6-C12亚芳基例如为邻-、间-或对-亚苯基、1,4-亚萘基或4,4′-二亚苯基。亚芳基的其它实例为亚苯基、亚萘基、亚联苯基、亚联苯基醚和亚蒽基。
术语“亚芳烷基”例如为其中脂族烃基和芳基烃基可以未被取代或取代的亚苄基。亚芳烷基可以未被取代或被C1-C4烷基或C1-C4烷氧基,或在亚烷基上具有2-12个氧乙烯单元和2-6个C原子的聚氧乙烯取代。
术语“卤素”意指氟、氯、溴和碘。
C1-C4烷基通常为线性或支化的。例如C1-C4烷基可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
C1-C4卤代烷基为在烷基上由卤素,例如1-3个或一个或两个卤素取代基单-或多取代的C1-C4烷基。实例为氯甲基、三氯甲基、二氟甲基、三氟甲基或2-溴丙基。
C1-C4烷氧基的实例为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基或叔丁氧基。
将式(I)增粘单体以约0.1-20重量%,约0.5-10重量%,或约1-10重量%的量加入涂料、膜或粘合剂组合物中。
当在放置预聚物组合物以前用式(I)增粘剂处理表面时,可将增粘剂例如溶于溶剂中并直接施涂在表面上。在这种情况下,增粘单体无论如何可占溶液的0.1-50重量%。
此外,可将表面用增粘单体处理并将其它增粘单体加入预聚物中并固化。
还设计使上述式(I)增粘单体聚合形成低聚物,然后使用形成的低聚物作为聚合添加剂,然后可使其与(甲基)丙烯酸酯预聚物结合。
使式(I)增粘单体预聚在几个方面是有利的。首先,增粘聚合添加剂然后很少可从固化的聚合基质中浸析。其次,聚合添加剂可以与预固化和后固化的聚合基质更相容。
预聚物
通常,所有可辐照固化的低聚物适用作预聚物。例如,分子量为至少500,例如约500-10,000,约700-10,000,约1,000-8,000或约1,000-7,000的低聚物为合适的。例如含有至少一个不饱和基团的氨基甲酸酯低聚物为合适的。例如,可辐照固化的低聚物可具有2、3、4、5或6个末端官能团。涂层可不仅含有一种具体预聚物或低聚物,而且可含有不同低聚物的混合物。合适的低聚物的制备为本领域技术人员已知的,例如公布于美国专利No.6,136,880中,在此引入作为参考。
预聚物的实例为聚不饱和化合物,例如(甲基)丙烯酸酯化的环氧树脂、(甲基)丙烯酸酯化或含有乙烯基醚或环氧基团的聚酯、聚氨酯和聚醚。
合适的还有具有一个或多个可自由基聚合的双键的化合物。这种化合物中可自由基聚合的双键优选为(甲基)丙烯酰基形式。在这里和下文中,(甲基)丙烯酰基和(甲基)丙烯酸基分别意指丙烯酰基和/或甲基丙烯酰基,和丙烯酸基和/或甲基丙烯酸基。至少两个(甲基)丙烯酰基形式的可聚合双键优选含在分子中。所述化合物可例如为聚(甲基)丙烯酸酯的(甲基)丙烯酰基官能低聚和/或聚合化合物。优选含有(甲基)丙烯酰基形式的可自由基聚合双键的化合物可通过常规方法,例如通过聚(甲基)丙烯酸酯与(甲基)丙烯酸反应而获得。这些和其它制备方法描述于文献中且为本领域技术人员已知的。
可辐照固化树脂的(甲基)丙烯酸酯预聚物组分例如为环氧(甲基)丙烯酸酯、脂族氨基甲酸酯(甲基)丙烯酸酯、芳族氨基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯和丙烯酸(甲基)丙烯酸酯。
预期以上预聚物的混合物。例如,芳族和脂族氨基甲酸酯(甲基)丙烯酸酯的混合物、环氧树脂(甲基)丙烯酸酯与脂族和/或芳族氨基甲酸酯(甲基)丙烯酸酯的混合物是可能的。具体混合物将由最终应用和具体应用所需的性能决定。
不饱和低聚物可以为不饱和聚酯树脂,其通常由马来酸、邻苯二甲酸和一种或多种二醇产生且分子量为约500-3000。另外,也可使用乙烯基醚单体和低聚物,以及具有聚酯、聚氨酯、聚醚、聚乙烯醚和环氧化物主链的马来酸酯封端的低聚物。如US 5,334,455所述带有乙烯基醚基团的低聚物和聚合物的组合尤其合适,在此将其引入作为参考,但也考虑用乙烯基醚官能化的单体和马来酸的共聚物。
氨基甲酸酯(甲基)丙烯酸酯化的低聚物为优选的预聚物。
脂族氨基甲酸酯特别好地用于其中要求韧性、挠性和良好室外耐久性的不变黄应用中。
芳族氨基甲酸酯丙烯酸酯在不要求抗发黄性的应用中提供韧性和挠性。
如本文所用,术语“脂族氨基甲酸酯丙烯酸酯”意欲具有本领域通常理解的含义,即由脂族二异氰酸酯或多异氰酸酯,即其中异氰酸酯基团由脂族骨架连接的二异氰酸酯制备的氨基甲酸酯丙烯酸酯。在一个实施方案中,例如脂族氨基甲酸酯丙烯酸酯包含至少一个选自三羟甲基丙烷、甘油、季戊四醇和二季戊四醇的多羟基化合物的残基。也可使用一种或多种六官能氨基甲酸酯丙烯酸酯和甲基丙烯酸酯,其中术语“六官能”应当理解意指丙烯酸酯包含具有6个丙烯酸酯基团的低聚物。可用于本发明中的市售脂族氨基甲酸酯丙烯酸酯的实例包括但不限于:由Cytec Industries市购的EBECRYL 244(用1,6-己二醇二丙烯酸酯稀释10%的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 264(用1,6-己二醇二丙烯酸酯稀释15%的脂族氨基甲酸酯三丙烯酸酯)、EBECRYL 265(具有25%三丙二醇二丙烯酸酯的脂族氨基甲酸酯三丙烯酸酯)、EBECRYL 270(具有小于10%三丙二醇二丙烯酸酯的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 284(用1,6-己二醇二丙烯酸酯稀释10%的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 1290(脂族氨基甲酸酯六丙烯酸酯)、EBECRYL 4830(具有10%四乙二醇二丙烯酸酯的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 4833(具有10%N-乙烯基-2-吡咯烷酮的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 4866(具有30%三丙二醇二丙烯酸酯的脂族氨基甲酸酯三丙烯酸酯)、EBECRYL 8210(不具有稀释剂的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 8301(不具有稀释剂的脂族氨基甲酸酯六丙烯酸酯)、EBECRYL 8402(不具有稀释剂的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 8405(具有20%1,6-己二醇二丙烯酸酯的脂族氨基甲酸酯四丙烯酸酯)、EBECRYL 8411(具有20%丙烯酸异冰片基酯的脂族氨基甲酸酯二丙烯酸酯)、EBECRYL 8800(具有10%丙烯酸乙氧基乙氧基乙酯的脂族氨基甲酸酯丙烯酸酯)、EBECRYL 8800-20R(具有20%三丙二醇二丙烯酸酯和丙烯酸8-乙氧基乙氧基乙酯的脂族氨基甲酸酯丙烯酸酯)、EBECRYL 8804(不具有稀释剂的脂族氨基甲酸酯二丙烯酸酯)和EBECRYL 8807(不具有稀释剂的脂族氨基甲酸酯二丙烯酸酯);由Exton,PA的Sartomer Corp.市购的Sartomer CN-961E75(用25%乙氧基化三羟甲基丙烷三丙烯酸酯配混的脂族氨基甲酸酯二丙烯酸酯)、CN-961H81(用19%丙烯酸2-(2-乙氧基乙氧基)乙酯配混的脂族氨基甲酸酯二丙烯酸酯)、CN-963A80(用20%三丙二醇二丙烯酸酯配混的脂族氨基甲酸酯二丙烯酸酯)、CN-964(脂族氨基甲酸酯二丙烯酸酯)、CN-966A80(用20%三丙二醇二丙烯酸酯配混的脂族氨基甲酸酯二丙烯酸酯)、CN-982A75(用25%三丙二醇二丙烯酸酯配混的脂族氨基甲酸酯二丙烯酸酯)和CN-983(脂族氨基甲酸酯二丙烯酸酯);由Chicago,Illinois的TAB Chemicals市购的TAB FAIRAD 8010、8179、8205、8210、8216、8264、M-E-15、UVU-316;和由Versaille,Missouri的Echo Resins市购的Echo Resin ALU-303;和由Aurora,Illinois的Rahn Radiation Curing市购的Genomer 4652。本文也可使用这些原料的组合。
芳族氨基甲酸酯通常理解为意指由芳族二异氰酸酯或多异氰酸酯,即其中异氰酸酯基团由芳族骨架连接的二异氰酸酯制备的氨基甲酸酯丙烯酸酯。
可用于本发明中的市售芳族氨基甲酸酯丙烯酸酯的实例包括但不限于:由Cytec Industries市购的EBECRYL 220(芳族氨基甲酸酯六丙烯酸酯)、EBECRYL 4827(芳族氨基甲酸酯二丙烯酸酯)、EBECRYL 4849(具有15%1,6-己二醇二丙烯酸酯的芳族氨基甲酸酯二丙烯酸酯)和EBECRYL6602-20T(芳族氨基甲酸酯三丙烯酸酯)。
市售的环氧丙烯酸酯、脂族和芳族氨基甲酸酯丙烯酸酯的组合、聚酯丙烯酸酯化和丙烯酸丙烯酸酯的实例可在由Cytec Industries可得并在2006年出版的RADCURE Energy Curable Resins,Product Guide-Coatings and Inks中找到,在此将其引入作为参考。实例包括但不限于:由Cytec Industries市购的EBECRYL 600(双酚A环氧二丙烯酸酯)、EBECRYL 605(双酚A环氧二丙烯酸酯)、EBECRYL 645(改性双酚A环氧二丙烯酸酯)、EBECRYL 860(环氧化豆油四丙烯酸酯)、EBECRYL3200(低粘度环氧丙烯酸酯)、EBECRYL 3411(脂肪酸改性的环氧二丙烯酸酯)、EBECRYL 3600(胺改性的环氧二丙烯酸酯)和EBECRYL 3720(双酚A环氧二丙烯酸酯);和由Sartomer市购的CN104(双酚A环氧二丙烯酸酯)、CN108(芳族环氧丙烯酸酯)、CN 109(双酚A环氧丙烯酸酯)、CN133(三官能脂族环氧丙烯酸酯)和CN186(芳族环氧丙烯酸酯)。
预聚物将构成例如涂料、膜或粘合剂总重量的约20-98重量%,约30-90重量%或约20-80重量%。
稀释剂
就本发明而言,稀释剂为可以以控制涂料配制剂粘度的方式使用的可辐照固化单体。因此,可使用具有至少一个能光引发聚合的官能团的低粘度单体。可例如选择加入的稀释剂的量以调整粘度为1,000-10,000mPas范围,即通常例如使用约10-90重量%或约10-80重量%。如果预聚物具有允许容易处理的粘度,则也可不加入稀释剂。单体稀释剂的官能团例如与低聚物组分如(甲基)丙烯酸酯的相同。
典型的稀释剂包括但不限于二丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇丙氧基化物二丙烯酸酯、三丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、双酚A乙氧基化物二丙烯酸酯、丙烯酸酯化二季戊四醇、丙氧基化甘油三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、三羟甲基丙烷乙氧基三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、烷氧基化三丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、聚醚四丙烯酸酯和丙氧基化甘油三丙烯酸酯。
其它烯属不饱和单体
预聚物可与其它烯属不饱和单体组合。涂料配制剂的烯属不饱和化合物(b)通常含有一个或多个烯键式双键。它们可以为低分子量(单体)或较高分子量(低聚)的,例如US 7,084,183所公开的,将其全部引入作为参考。
具有双键的单体的实例为烷基和羟基烷基丙烯酸酯和甲基丙烯酸酯,例如丙烯酸甲基、乙基、丁基、2-乙基己基和2-羟乙基酯、丙烯酸异冰片基酯,和甲基丙烯酸甲基和乙基酯。其它实例为丙烯腈、丙烯酰胺、甲基丙烯酰胺、N-取代的(甲基)丙烯酰胺、乙烯基酯如乙酸乙烯酯、乙烯基醚如异丁基乙烯基醚、苯乙烯、烷基-和卤代-苯乙烯、N-乙烯基吡咯烷酮、氯乙烯和偏二氯乙烯。
具有多个双键的单体的实例为乙二醇二丙烯酸酯、丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、六亚甲基二醇二丙烯酸酯和双酚A二丙烯酸酯、4,4′-双(2-丙烯酰氧基乙氧基)二苯基丙烷、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯和季戊四醇四丙烯酸酯、丙烯酸乙烯酯、二乙烯基苯、琥珀酸二乙烯酯、邻苯二甲酸二烯丙酯、磷酸三烯丙酯、异氰脲酸三烯丙酯和异氰脲酸三(2-丙烯酰基乙基)酯。
任选添加剂
涂料、膜或粘合剂组合物还可包含根据需要改变或增强某些性能,例如改善耐气候性的各种添加剂,改善抗磨性的组分、增强外观的添加剂和改善韧性和机械性能的材料。可用于本发明涂料组合物中的添加剂的实例包括但不限于光引发剂、滑爽剂、流平剂、润湿剂、增粘剂、防吸收剂、消泡剂,例如泡沫破坏聚合物与聚硅氧烷的混合物、促进剂、颜料分散助剂、防粘连剂、防烧结剂、防滑剂、防结皮剂、抗静电剂、抗剥落剂、粘合剂、固化剂、除气剂、稀释剂、分散剂、干燥剂、乳化剂、填料、平光剂、流动调节剂、光泽剂、硬化剂、润滑剂、抗划伤助剂、增白剂、增塑剂、溶剂、稳定剂、表面活性剂、粘度改进剂、UV稳定剂、UV吸收剂、和防水剂。例如,涂料组合物还可包含分散于其中的细碎SiO2、Al2O3、ZrO2或TiO2。这些原料可改进涂料的粘度使得它可容易地施涂并可增强固化涂层的抗磨性。
固化剂
增粘单体可通过常规方法如辐照、热或氧化还原固化与其它乙烯基单体或预聚物聚合以形成涂料、膜或粘合剂。
就本发明而言,辐照包括紫外线、可见光和红外光以及电子束引发。
当组合物借助紫外线、可见光、红外或电子束引发而固化时,固化剂通常为光引发剂。
光引发剂
可使用任何已知的光引发剂。例如单-或双-酰基氧化膦类,如二苯基-2,4,6-三甲基苯甲酰基氧化膦或双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基苯基氧化膦;α-羟基酮类,例如1-羟基环己基苯基酮或2-羟基-1-[4-(2-羟基乙氧基)苯基]-2-甲基-1-丙酮;α-氨基酮类,例如2-甲基-1-[4-(甲硫基)苯基]-2-(4-吗啉基)-1-丙酮、2-苄基-2-(二甲基氨基)-1-[4-(4-吗啉基)苯基]-1-丁酮、2-(4-甲基苄基-2-(二甲基氨基)-1-[4-(4-吗啉基)苯基]-1-丁酮或2-苄基-2-(二甲基氨基)-1-[3,4-二甲氧基苯基]-1-丁酮;二苯甲酮类,例如二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮、2-甲基二苯甲酮、2-甲氧基羰基二苯甲酮、4,4’-双(氯甲基)二苯甲酮、4-氯二苯甲酮、4-苯基二苯甲酮、4,4’-双(二甲基氨基)二苯甲酮、4,4’-双(二乙基氨基)二苯甲酮、2-苯甲酰基苯甲酸甲基酯、3,3’-二甲基-4-甲氧基二苯甲酮、4-(4-甲基苯基硫基)二苯甲酮、2,4,6-三甲基-4’-苯基-二苯甲酮或3-甲基-4’-苯基-二苯甲酮;缩酮化合物,例如2,2-二甲氧基-1,2-二苯基-乙酮;和单体或二聚苯基乙醛酸酯,例如甲基苯基乙醛酸酯、5,5’-氧代-二(乙烯氧基二羰基苯基)或1,2-(苯甲酰基羧基)乙烷。
预期光引发剂的混合物。特别是使用如美国专利No.7,169,826所述双酰基氧化膦光引发剂与单酰基氧化膦光引发剂的混合物或α-羟基酮引发剂与双酰基氧化膦的混合物,在此将其全部引入作为参考。
2007年10月17日提交并全部引入作为参考的未决临时美国申请No.60/999,361中公开的光引发剂特别有意义。60/999,361公开的光引发剂为α-羟基酮光引发剂且具有化学结合的增粘剂基团如羧酸、膦酸酯或三烷氧基硅烷。当将增粘光引发剂掺入涂料、膜或粘合剂中时,涂料强力附着在金属表面上且有效作为金属底漆。
令人惊讶的是,发明人已发现通过将具有化学结合的增粘剂基团如羧酸的α-羟基酮光引发剂与增粘单体(式I)结合在环氧基涂料、膜或粘合剂组合物中可以以相当改善的粘合用于基质如铝或钢上。由于将预期增粘单体和增粘光引发剂增加对金属的粘合,当二者结合时观察到对金属粘合的协同增效改善,这是令人惊讶的。这在环氧树脂基体中的铝基质上尤其显著。
重要的α-羟基酮光引发剂为由式II或III羧酸取代的那些:
其中:
G2和G3独立地为C1-C4烷基或共同形成1,5-亚戊基,
D为-R1-COOH,
R1为可进一步被-OH或-COOH取代的支化或非支化C1-C6烷基,
R为C1-C6亚烷基、C1-C6亚烷基氧基或被1或2个氧原子间隔的C4-C6亚烷基,
A为选自-(O)s-C(=O)G和-O-CH2-C(=O)G的基团,
G选自各自被1-3个-COOH,或一个或两个
-C(=O)-O-CH2-C(CH3)(CH2OH)-COOH取代的苯基和萘基,且
s为0或1。
为增强光引发剂的性能,配制剂还可包含敏化剂化合物,例如胺。
通常用于本发明中的光引发剂基于组合物总重量为约0.1-10重量%,优选约1-5重量%。
辐照固化
当本发明涂料组合物的固化或聚合可热实现时,有利地通过辐照固化涂料组合物。本领域技术人员应当理解尽管主要通过辐照能固化,但可辐照固化涂料也可通过加热固化或可通过加热促进它们的固化。固化可通过任何能产生自由基的电离辐照源引发,包括γ辐照、红外线、微波,但通常通过电子束或紫外辐照引发。
在一个实施方案中,例如涂料组合物通过曝露在通常为200-400nm波长范围的紫外辐照下而固化。当聚合通过紫外辐照引发时,涂料组合物将根据已知的UV固化组合物的实践通常包括光引发剂。
用辐照固化可在氮气下或在空气的存在下进行。
固化也可在绝氧环境中进行。
通常Hg中压灯或/和Fusion D灯用于实现UV固化。闪光灯也是合适的。显然灯的发射与所用光引发剂或光引发剂混合物的吸收相配。
将抑制剂如氢醌、对甲氧基苯酚和螯合剂掺入液体绝氧粘合剂中以防止在运输和储存期间过早聚合。
涂料、膜或粘合剂作为液体或固体如作为粉末施用。
由于它们更容易地施涂在表面或基质上,液体组合物可例如为优选的。
本发明组合物可以为溶剂基或水基体系,其中式(I)增粘单体与(甲基)丙烯酸酯预聚物组合确保对金属粘合的改善。
就本发明而言,水基意指其中水为组合物主要量的涂料、膜或粘合剂组合物。水可以为唯一的溶剂和/或乳化剂。然而,除水外,组合物还可含有机溶剂。
组合物的水含量主要取决于所需的组合物固体含量。优选的组合物含约5-80重量%水且可为乳液、分散体或溶液。
涂料、膜或粘合剂可经由任何本领域已知的方法施涂在表面上。
例如涂料可通过常规技术,例如喷雾、浸渍、涂布或电沉积施涂在基质上。在许多情况下,可施涂多个涂层。
以下实施例描述本发明某些实施方案。应当理解可根据本文的公开内容不偏离本发明的精神或范围地对公开的实施方案作出大量改变。因此,这些实施例不意欲限制本发明的范围。而是,仅通过附属权利要求和它们的等价物确定本发明的范围。
1H和31P NMR光谱在室温下记录在300MHz Gemini分光计上。
实施例1
3-丙烯酰氧基丙基膦酸
将亚磷酸三乙酯(122.8g;0.74摩尔)和1,3-二溴丙烷(751.9g;3.72摩尔)在室温下在装配有回流冷凝器的圆底烧瓶中混合并机械搅拌。将混合物在油浴中在160℃下加热30分钟,然后冷却并通过真空蒸馏分馏。第一收集的馏分为过量的1,3-二溴丙烷。3-溴丙基膦酸二乙酯在109-111℃和0.77毫巴下蒸馏。
将3-溴丙基膦酸二乙酯(124.25g;0.48摩尔)、丙烯酸钾(54.0g;0.49摩尔)和DMF(150ml)装入装配有机械搅拌器、温度计和冷凝器的三颈烧瓶中。将反应物料在80℃下搅拌3小时,冷却至室温并过滤。将粗产物倒入水中,用乙醚萃取并用含水NaHCO3洗涤。经MgSO4干燥,其后在真空下蒸发溶剂,得到作为清澈无色液体的3-丙烯酰氧基丙基膦酸二乙酯(110g;收率92%)。1H NMR(CDCl3,δppm)1.32(t,6H,2CH 3-CH2),1.76-1.89(m,2H,CH2-CH 2-P),1.92-2.05(m,2H,CH 2-CH2-P),4.04-4.16(m,4H,2CH3-CH 2),4.2(t,2H,CH2-O-C(O)),5.83(dd,1H,CH=),6.11(dd,1H,CH=),6.41(dd,1H,CH=)。31P NMR(CDCl3,δppm)29.49。
在室温下向3-丙烯酰氧基丙基膦酸二乙酯(31.12g;0.124摩尔)的CH2Cl2(85g)溶液中逐滴加入三甲基溴硅烷(40g;0.261摩尔)的CH2Cl2(9.2g)溶液。使混合物回流4小时。将溶剂在旋转式蒸发器上减压蒸馏以提供作为清澈无色液体的二(三甲基甲硅烷基)3-丙烯酰氧基丙基膦酸酯(42.4g;GC纯度95%)。1H NMR(CDCl3,δppm)0.006(s,9H,CH3-Si),1.4-1.54(m,2H,CH2-P),1.59-1.72(m,2H,CH 2-CH2-),3.91(t,2H,CH2-O),5.55(dd,1H,CH=),5.83(dd,1H,CH=),6.12(dd,1H,CH=)。31P NMR(CDCl3,δppm)13.55。
将二(三甲基甲硅烷基)3-丙烯酰氧基丙基膦酸酯(40g;0.118摩尔)溶于MeOH(130ml)中。将溶液在室温下搅拌2小时。将溶剂在旋转式蒸发器上真空蒸馏以提供作为高粘性无色油的产物,其在几天储存以后变成固体(22.7g;收率99%)。1H NMR(DMSO-d6,δppm)1.78-2.00(m,4H,CH2-CH2-P),4.20(t,2H,CH2-O),4.91(s,2H,(HO)2-P),5.94(dd,1H,CH=),6.16(dd,1H,CH=),6.39(dd,1H,CH=)。31P NMR(DMSO-d6,δppm)31.71。
实施例2
3-甲基丙烯酰氧基丙基膦酸
将3-溴丙基膦酸二乙酯(103.6g;0.4摩尔)、甲基丙烯酸钾(52.2g;0.42摩尔)和DMF(100ml)装入装配有机械搅拌器、温度计和冷凝器的三颈烧瓶中。将反应物料在80℃下搅拌3小时,冷却至室温并过滤。将粗产物倒入水中,用乙醚萃取并用含水NaHCO3洗涤。经MgSO4干燥,然后在真空下蒸发溶剂提供作为清澈无色液体的3-甲基丙烯酰氧基丙基膦酸二乙酯(96g;收率91%;在0.2毫巴下沸点94-96℃)。1H NMR(CDCl3,δppm)1.32(t,6H,2CH 3-CH2),1.75-1.88(m,2H,CH2-CH 2-P),1.91-2.05(m,2H,CH 2-CH2-P),1.93(s,3H,CH3),4.03-4.16(m,4H,2CH3-CH 2-O),4.18(t,2H,CH2-O-C(O)),5.56(s,1H,CH=),6.09(s,1H,CH=)。31P NMR(CDCl3,δppm)29.54。
在室温下向3-甲基丙烯酰氧基丙基膦酸二乙酯(28.2g;0.107摩尔)的CH2Cl2(60g)溶液中逐滴加入三甲基溴硅烷(34.4g;0.225摩尔)的CH2Cl2(22g)溶液。使混合物回流5小时。将溶剂在真空下蒸发以得到作为清澈无色液体的二(三甲基甲硅烷基)3-甲基丙烯酰氧基丙基膦酸酯(37.9g)。1HNMR(CDCl3,δppm)0.01(s,9H,CH3-Si),1.41-1.55(m,2H,CH2-P),1.59-1.73(m,2H,CH 2-CH2-P),1.66(d,3H,CH3),3.90(t,2H,CH2-O),5.28(s,1H,CH=),5.82(s,1H,CH=)。31P NMR(CDCl3,δppm)13.6。
将二(三甲基甲硅烷基)3-甲基丙烯酰氧基丙基膦酸酯(34.0g;0.096摩尔)溶于甲醇(115ml)中。将溶液在室温下搅拌2小时。将溶剂在旋转式蒸发器上真空蒸馏以提供作为高粘性无色油的3-甲基丙烯酰氧基丙基膦酸(19.9g;收率99%)。1H NMR(DMSO-d6,δppm)1.52-1.66(m,2H,CH2-P),1.74-1.93(m,2H,CH 2-CH2-P),1.87(s,3H,CH3),4.12(t,2H,CH2-O),5.66(s,1H,CH=),6.02(s,1H,CH=)。31P NMR(DMSO-d6,δppm)27.06。
应用实施例
制备光固化树脂:
脂族氨基甲酸酯树脂EBECRYL 8804和环氧树脂EBECYRL 605(Cytec Industries提供)用于该研究中以量化本发明增粘剂对光固化树脂在金属表面上的粘合的影响。
将两种树脂用活性稀释剂1,6-己二醇二丙烯酸酯(HDDA)稀释成80%树脂与20%稀释剂的混合物以降低粘度。
表1所示配制剂系列用两种树脂制备用于稍后的施涂(draw-down)和UV固化。数表示基于重量的份/整体。该研究中所用的对照增粘剂为源自Johoku Chemicals的商业单体JPA-514或2-羟乙基甲基丙烯酸酯酸磷酸酯。该磷酸酯单体还可由其他公司如Rhodia(Sipomer PAM-100)、Kowa或Sartomer(CD9050)市购。本文中对照单体与实施例1的增粘单体比较。
表1
1由用25%TPGDA稀释的75%双酚A环氧二丙烯酸酯组成的树脂。
2脂族氨基甲酸酯二丙烯酸酯树脂。
31,6-己二醇二丙烯酸酯。
4Irgacure 500为二苯甲酮与Irgacure 184或1-羟基环己基苯基酮的1∶1重量比混合物。
5光引发剂1为3,3’-双[{2-[4-(1-羟基环己基羰基)苯基]乙氧基}羰基]二苯甲酮-4,4’-二羧酸。
6光引发剂2为3-[4-((1-羟基环己基)羰基))苯基]-3-苯基丙酸。
7光引发剂3为光引发剂2与Irgacure 500的1∶2.5重量比混合物。
在将各个组分结合以后,将所有配制剂摇动过夜以确保完全均匀性。注意防止曝露在环境光和湿气下。
将配制剂施涂在金属基质上并UV固化:
两种金属基质铝和冷轧钢用于该研究中以阐明在不同金属表面上的增粘能力的差别。铝板(#3003;磨光大小03×04×025)和冷轧钢板(未磨光大小03×04×025)购自ACT laboratories用作固化基质。将板表面用甲醇冲洗,用无尘擦布清洁并用空气干燥以确保清洁表面。
对于目标1密耳的湿厚度,用Gardco Automatic Drawdown Machine(施涂机器)以1.5英寸/秒的速度、6英寸的行程长度和#10棒将树脂施涂在基质表面上。将各个配制剂施涂在铝和冷轧钢基质板上。在施涂以后,使用Fusion UV固化灯将板UV固化。使各个板以17ft/min的速率通过9mm×6英寸H-灯泡(Hg蒸气)下三次。在UV曝露以后,在进行划格法分析以前使基质固化过夜。
光固化树脂的划格法试验
将基质用装有2mm划格器的BYK Gardner-Cross-Cut-Tester Kit横切。将树脂垂直刻划以形成具有36个2mm×2mm格的8×8十字划痕。在刻划以后,使用刮刀将透明胶带(3M胶带#10)压在十字划痕格上以确保均匀附着。随着迅速的均匀牵引运动,将胶带快速地剥离基质。粘合表示为树脂未被胶带剥离的总十字划痕表面的百分数(ISO & DIN 2409)。因此,较高的百分数表示较好的粘合。视觉评估表面固化程度。粘合数据和观察呈现于表2中。
表2
实验数据显示对于同一树脂类型,在金属表面上的粘合可取决于增粘剂和光引发剂的选择由差至良好至优异变化。所用两种增粘剂JPA-514和实施例1的膦酸丙烯酸酯通过自由基聚合直接掺入树脂中。含磷侧官能团、JPA-514和实施例1中的膦酸中的酸磷酸酯具有附着在金属表面上的能力,因此提高粘合。在大多数情况下,当使用促进剂时粘合改善,当使用实施例1的膦酸丙烯酸酯时具有清楚的粘合显著提高的倾向。
项1-3、7-9、13-15和19-21的环氧基树脂不能特别好地粘附在铝上。当将JPA-514加入UV固化配制剂中时获得最小或无粘合改善。然而,在大多数情况下实施例1的新增粘剂始终提高在铝上的粘合达22%树脂保留在十字划痕的金属基质上。在冷轧钢基质上,JPA-514提高粘合至30%树脂保留的最大值,而实施例1的新膦酸丙烯酸酯在所有情况下显著改善粘合至70-100%树脂保留。
将含磷单体加入项4-6、10-12、16-18和22-24的脂族氨基甲酸酯基树脂中显著地改善固化涂层的附着性能。在铝上,JPA-514提高粘合至50-95%树脂保留,而实施例1的新增粘剂在所有情况下获得接近100%粘合。在冷轧钢基质上,磷酸酯和膦酸单体获得优异的粘合。
当使用用能参与与金属基质相互作用的羧酸基团化学改性的光引发剂PI 1时,观察到粘合改善效果。在氨基甲酸酯基树脂中该效果特别显著,其中它分别提高粘合至铝上十字划痕涂层的75%保留和冷轧钢上93%保留。
Claims (17)
1.一种在表面上的涂料、膜或粘合剂组合物,所述涂料、膜或粘合剂包含:
a)至少一种(甲基)丙烯酸酯预聚物,
b)式(I)增粘单体或其混合物:
Q为至少一个选自一个或多个线性或支化C1-C10烷基、线性C1-C18亚烷基、C6-C12亚芳基或线性或支化亚芳烷基的二价连接基团;
其中线性或支化C1-C10烷基、C6-C12亚芳基、线性或支化亚芳烷基连接基团未被取代或被一个或多个C1-C4烷基、C1-C4卤代烷基、卤素、羟基或C1-C4烷氧基取代;
或
Q为被一个或多个-O-、-S-、-O(CO)-、-S(CO)-、-OC(O)O-或-C(O)-间隔的C2-C12亚烷基;
m为1-2;
n为1-2;
R1和R2独立地为氢或线性或支化C1-C4烷基;
R4和R5独立地为氢或线性或支化C1-C4烷基;
和
c)固化剂。
2.根据权利要求1的组合物,其中所述(甲基)丙烯酸酯预聚物为脂族或芳族氨基甲酸酯(甲基)丙烯酸酯或环氧(甲基)丙烯酸酯。
3.根据权利要求1或2的组合物,其中所述(甲基)丙烯酸酯预聚物为脂族氨基甲酸酯(甲基)丙烯酸酯。
4.根据权利要求1-3中任一项的组合物,其中R4和R5独立地为氢。
5.根据权利要求1-4中任一项的组合物,其中预聚物为脂族氨基甲酸酯(甲基)丙烯酸酯。
6.根据权利要求1-5中任一项的组合物,其中Q为C3-C18亚烷基。
7.根据权利要求1-6中任一项的组合物,其中固化剂为光引发剂。
9.一种包含根据权利要求1-8中任一项所述组合物的在表面上的辐照固化的涂料、膜或粘合剂。
10.根据权利要求9的辐照固化的涂料、膜或粘合剂,其中表面为金属且金属为铝或钢。
11.根据权利要求10的辐照固化的涂料、膜或粘合剂,其中所述金属为挠性的。
12.一种改善涂料、膜或粘合剂对表面的粘合的方法,所述方法包括以下步骤:
i)用式(I)增粘单体处理表面:
Q为至少一个选自一个或多个线性或支化C1-C10烷基、线性C1-C18亚烷基、C6-C12亚芳基或线性或支化亚芳烷基的二价连接基团;
其中线性或支化C1-C10烷基、C6-C12亚芳基、线性或支化亚芳烷基连接基团未被取代或被一个或多个C1-C4烷基、C1-C4卤代烷基、卤素、羟基或C1-C4烷氧基取代;
或
Q为被一个或多个-O-、-S-、-O(CO)-、-S(CO)-、-OC(O)O-或-C(O)-间隔的C2-C12亚烷基;
m为1-2;
n为1-2;
R1和R2独立地为氢或线性或支化C1-C4烷基;
R4和R5独立地为氢或线性或支化C1-C4烷基;
将包含(甲基)丙烯酸酯预聚物和光引发剂的组合物施涂在所述处理的表面上;
或
将包含上述式(I)增粘单体、(甲基)丙烯酸酯预聚物和光引发剂的组合物施涂在表面上;
或
使上述式(I)增粘单体聚合形成增粘低聚物,
将所述低聚物加入(甲基)丙烯酸酯预聚物和光引发剂中,
和
ii)辐照。
13.根据权利要求12的方法,其中所述(甲基)丙烯酸酯预聚物为脂族或芳族氨基甲酸酯(甲基)丙烯酸酯或环氧树脂。
14.根据权利要求12或13的方法,其中所述(甲基)丙烯酸酯预聚物为脂族或芳族氨基甲酸酯(甲基)丙烯酸酯。
15.根据权利要求12-14中任一项的方法,其中所述(甲基)丙烯酸酯预聚物为脂族氨基甲酸酯(甲基)丙烯酸酯。
16.根据权利要求12-15中任一项的方法,其中R4和R5独立地为氢。
17.根据权利要求12-16中任一项的方法,其中Q为C3-C18亚烷基。
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CN104302720A (zh) * | 2012-04-27 | 2015-01-21 | 荒川化学工业株式会社 | 紫外线固化型粘合剂组合物及粘合层 |
CN104822694A (zh) * | 2012-12-05 | 2015-08-05 | 罗门哈斯公司 | 用于制备膦酸单体的方法 |
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Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008053990A1 (fr) * | 2006-11-02 | 2008-05-08 | Kabushiki Kaisha Shofu | Composition dentaire à un seul composant contenant un agent de couplage de type silane et un monomère polymérisable contenant un groupe acide |
WO2010071956A1 (en) | 2008-12-22 | 2010-07-01 | Canadian Bank Note Company, Limited | Improved printing of tactile marks for the visually impaired |
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JP6022871B2 (ja) * | 2012-09-26 | 2016-11-09 | 株式会社オートネットワーク技術研究所 | 接着性光硬化組成物及びその製造方法 |
CA2885432C (en) | 2012-09-28 | 2017-04-25 | Dow Global Technologies Llc | Process for the production of high purity glycol esters |
JP2016525154A (ja) * | 2013-06-24 | 2016-08-22 | ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング | 接着強化添加剤およびそれを含むコーティング組成物 |
KR20160022815A (ko) | 2013-06-24 | 2016-03-02 | 다이니폰 인사츠 가부시키가이샤 | 수지 조성물 |
JP6536344B2 (ja) * | 2015-10-13 | 2019-07-03 | 横浜ゴム株式会社 | シーリング材用水系プライマー組成物 |
US10392337B2 (en) | 2015-10-14 | 2019-08-27 | Dow Global Technologies Llc | Process for purification of methyl methacrylate |
EP3604318B1 (en) | 2017-03-31 | 2024-01-17 | Mitsui Chemicals, Inc. | Phosphorus-containing compound |
US11912801B2 (en) | 2018-08-30 | 2024-02-27 | 3M Innovative Properties Company | (Meth)acrylate urethane (urea) phosphonates as adhesion promoters |
EP3997167A1 (en) * | 2019-07-12 | 2022-05-18 | Henkel AG & Co. KGaA | Single layer autodepositable coating formulation |
JP7282651B2 (ja) * | 2019-10-16 | 2023-05-29 | ミヨシ油脂株式会社 | 重合性ホスホン酸系化合物及び接着性組成物 |
TW202224929A (zh) * | 2020-12-25 | 2022-07-01 | 律勝科技股份有限公司 | 積層板及其製造方法 |
KR20220100133A (ko) * | 2021-01-07 | 2022-07-15 | 삼성디스플레이 주식회사 | 수지 조성물 및 수지 조성물로부터 형성된 접착층을 포함하는 표시 장치 |
WO2024091400A1 (en) | 2022-10-25 | 2024-05-02 | Sun Chemical Corporation | Primers for energy-curable inks and coatings on metallized substrates |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2934555A (en) | 1957-12-12 | 1960-04-26 | Rohm & Haas | Dialkylphosphonoalkyl acrylates and methacrylates and process for preparing same |
US3030347A (en) | 1960-04-25 | 1962-04-17 | Rohm & Haas | Dialkylphosphonoalkyl acrylate and methacrylate copolymers |
DE2344197A1 (de) | 1973-09-01 | 1975-03-27 | Dynamit Nobel Ag | Funktionelle organophosphonsaeureester als konservierende haftvermittler oder ueberzuege fuer metalle |
US4526728A (en) | 1982-03-24 | 1985-07-02 | Hoechst Aktiengesellschaft | 2-Acrylamido- and 2-methacrylamido-2-methyl propanephosphonic acids and their salts, process for the preparation thereof, and use thereof for the manufacture of copolymers |
US4658003A (en) * | 1984-07-02 | 1987-04-14 | The Dow Chemical Company | Novel phosphinyl-containing ethylenically unsaturated compounds |
US4738870A (en) | 1986-03-27 | 1988-04-19 | The Dow Chemical Company | Adherent photopolymerizable compositions |
JPS63182380A (ja) * | 1987-01-23 | 1988-07-27 | Nitto Electric Ind Co Ltd | 被覆材組成物 |
DE3738567A1 (de) * | 1987-03-12 | 1988-09-22 | Merck Patent Gmbh | Coreaktive fotoinitiatoren |
US5334455A (en) | 1988-08-12 | 1994-08-02 | Stamicarbon B.V. | Free-radical curable compositions |
JPH05186620A (ja) | 1992-01-13 | 1993-07-27 | Mitsubishi Rayon Co Ltd | 被覆成形物およびその製造方法 |
JPH08225585A (ja) | 1995-12-20 | 1996-09-03 | Dow Chem Co:The | 新規なホスフィニル含有エチレン系不飽和化合物を含むポリマー組成物 |
DE19654642C2 (de) | 1996-12-28 | 2003-01-16 | Chemetall Gmbh | Verfahren zur Behandlung metallischer Oberflächen mit einer wässerigen Lösung |
DE19709280B4 (de) * | 1997-03-07 | 2004-03-04 | Heraeus Kulzer Gmbh & Co. Kg | Verfahren zur Herstellung von dekorierten metallischen Schmuckgegenständen und Verwendung einer photopolymerisierbaren Zusammensetzung zur Dekoration von metallischen Schmuckgegenständen m |
AU7084798A (en) | 1997-04-22 | 1998-11-13 | Dsm N.V. | Liquid curable resin composition |
KR20020074059A (ko) | 1999-06-11 | 2002-09-28 | 아토피나 | 금속의 부식을 방지하는 방식과 비오염 반응성 혼합물의사용 |
FR2815633B1 (fr) * | 2000-10-24 | 2004-01-09 | Atofina | Procede de preparation de (meth) acrylate de (dialkylphosphono) alkyle |
US20040266906A1 (en) | 2001-10-26 | 2004-12-30 | Joachim Klee | Hydrolysis stable self-etching,self-priming adhesive |
TWI312786B (en) | 2001-11-08 | 2009-08-01 | Ciba Sc Holding Ag | Novel difunctional photoinitiators |
DE10300751A1 (de) * | 2003-01-11 | 2004-07-22 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen, Beschichtungszusammensetzung und derart hergestellte Überzüge |
CN1842504B (zh) | 2003-08-29 | 2010-12-08 | 西巴特殊化学品控股有限公司 | 光纤涂料 |
DE602005002656T2 (de) * | 2004-04-19 | 2008-07-17 | Ciba Specialty Chemicals Holding Inc. Patent Departement | Neue photoinitiatoren |
DE102006045041A1 (de) * | 2006-09-25 | 2008-03-27 | Evonik Degussa Gmbh | Strahlenhärtbare Formulierung, die zu flexiblen Beschichtungen mit erhöhtem Korrosionsschutz auf Metalluntergründen führt |
WO2009050116A2 (en) | 2007-10-17 | 2009-04-23 | Basf Se | Adhesion promoting photoinitiators for uv cured coatings over metal surfaces |
-
2009
- 2009-10-21 CA CA 2739713 patent/CA2739713A1/en not_active Abandoned
- 2009-10-21 CN CN2009801431933A patent/CN102203200A/zh active Pending
- 2009-10-21 JP JP2011533678A patent/JP2012506929A/ja active Pending
- 2009-10-21 MX MX2011003670A patent/MX2011003670A/es active IP Right Grant
- 2009-10-21 WO PCT/EP2009/063768 patent/WO2010049322A2/en active Application Filing
- 2009-10-21 EP EP09736605A patent/EP2350215A2/en not_active Withdrawn
- 2009-10-21 US US12/582,862 patent/US8372516B2/en not_active Expired - Fee Related
- 2009-10-21 KR KR1020117009882A patent/KR20110079706A/ko not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104302720A (zh) * | 2012-04-27 | 2015-01-21 | 荒川化学工业株式会社 | 紫外线固化型粘合剂组合物及粘合层 |
CN104302720B (zh) * | 2012-04-27 | 2016-08-17 | 荒川化学工业株式会社 | 紫外线固化型粘合剂组合物及粘合层 |
CN104822694A (zh) * | 2012-12-05 | 2015-08-05 | 罗门哈斯公司 | 用于制备膦酸单体的方法 |
CN113265203A (zh) * | 2021-05-20 | 2021-08-17 | 常州百佳年代薄膜科技股份有限公司 | 抗蓝光胶膜、高剥离力抗蓝光胶膜及制备方法 |
Also Published As
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US8372516B2 (en) | 2013-02-12 |
WO2010049322A3 (en) | 2010-06-24 |
WO2010049322A2 (en) | 2010-05-06 |
EP2350215A2 (en) | 2011-08-03 |
CA2739713A1 (en) | 2010-05-06 |
JP2012506929A (ja) | 2012-03-22 |
MX2011003670A (es) | 2011-04-28 |
US20100112362A1 (en) | 2010-05-06 |
KR20110079706A (ko) | 2011-07-07 |
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