CN1864989A - 层压物、其生产及用途 - Google Patents
层压物、其生产及用途 Download PDFInfo
- Publication number
- CN1864989A CN1864989A CNA2006100802313A CN200610080231A CN1864989A CN 1864989 A CN1864989 A CN 1864989A CN A2006100802313 A CNA2006100802313 A CN A2006100802313A CN 200610080231 A CN200610080231 A CN 200610080231A CN 1864989 A CN1864989 A CN 1864989A
- Authority
- CN
- China
- Prior art keywords
- silane
- methyl
- laminate
- organosilan
- vinyl
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000853 adhesive Substances 0.000 claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 claims abstract description 53
- 238000004049 embossing Methods 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- -1 card Substances 0.000 claims description 80
- 239000006185 dispersion Substances 0.000 claims description 56
- 239000000178 monomer Substances 0.000 claims description 56
- 229910000077 silane Inorganic materials 0.000 claims description 53
- 229940117958 vinyl acetate Drugs 0.000 claims description 38
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000003475 lamination Methods 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011111 cardboard Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920006254 polymer film Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 8
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000123 paper Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical compound CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 claims description 6
- 229920001290 polyvinyl ester Polymers 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 claims description 4
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000012549 training Methods 0.000 claims description 3
- BVNZLSHMOBSFKP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxysilane Chemical compound CC(C)(C)O[SiH3] BVNZLSHMOBSFKP-UHFFFAOYSA-N 0.000 claims description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 claims description 2
- GXDZOSLIAABYHM-UHFFFAOYSA-N [diethoxy(methyl)silyl]methyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)COC(=O)C(C)=C GXDZOSLIAABYHM-UHFFFAOYSA-N 0.000 claims description 2
- YBUIRAZOPRQNDE-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)COC(=O)C(C)=C YBUIRAZOPRQNDE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- FIRQYUPQXNPTKO-UHFFFAOYSA-N ctk0i2755 Chemical class N[SiH2]N FIRQYUPQXNPTKO-UHFFFAOYSA-N 0.000 claims description 2
- KIZRJEKYMKLUAM-UHFFFAOYSA-N di(butan-2-yloxy)-ethenyl-methylsilane Chemical compound CCC(C)O[Si](C)(C=C)OC(C)CC KIZRJEKYMKLUAM-UHFFFAOYSA-N 0.000 claims description 2
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical group CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
- RVZXYYFNTDJNFG-UHFFFAOYSA-N ethenyl-methyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(C=C)OC(C)C RVZXYYFNTDJNFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004815 dispersion polymer Substances 0.000 abstract description 5
- 150000001282 organosilanes Chemical class 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract 1
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 25
- 239000003995 emulsifying agent Substances 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 239000012939 laminating adhesive Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- 229920001567 vinyl ester resin Polymers 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- 239000005026 oriented polypropylene Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000006735 epoxidation reaction Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012875 nonionic emulsifier Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004821 Contact adhesive Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- KACUYPDOCGVCEW-UHFFFAOYSA-N [SiH3]N.CO[Si](OC)(OC)CCCNCCN Chemical compound [SiH3]N.CO[Si](OC)(OC)CCCNCCN KACUYPDOCGVCEW-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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Abstract
本发明描述了一种层压物,所述层压物包括片状基材和通过粘合剂连接到基材上的膜,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷的粘合剂用于将聚合物膜粘合到多孔基材上和用于高光泽膜的层压的用途,该有机硅烷在聚合过程中引入到聚合物中和/或随后加入并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团。通过添加有机硅烷可以生产层压物,所述层压物可快速加工并且其特征在于改进了压纹强度。
Description
本发明涉及通过粘合选定的聚合物分散体生产的层压物。
在含水粘合剂制剂中使用聚合物水分散体作为粘合剂或胶粘剂对于本领域技术人员而言是已知的。与溶剂基粘合剂相比,这些聚合物分散体在使用它们时提供了避免溶剂散发的优点。由于有机溶剂通常可燃,甚至易于着火,上述种类的含水粘合剂还提供了在使用中显著的安全性的优点。
包含聚合物分散体和有机硅烷添加剂的粘合剂是已知的。EP-A-215,518描述了一种包含氨基硅烷的聚合物水散体。将分散体用作具有改进的湿强度的油漆或建筑用粘合剂。JP-A-10/178,931描述了包含环氧化硅烷化合物的乳液油漆。使用这些油漆生产的涂料显示出高的耐候性、耐化学品性和耐水性。US-A-2002/0037964描述了多异氰酸酯与选定的氨基硅烷的反应产物。其在底漆中可用作粘合促进剂。US-A-4,032,487公开了一种包含选定的丙烯酸酯共聚物和含有环氧化物和烷氧基硅烷官能团的交联剂的粘合剂组合物。US-A-2005/0038152描述了基于水分散体的压敏粘合剂,所述水分散体包含硅烷改性的聚丙烯酸酯和与硅烷偶联的化合物。该粘合剂易于与临时背膜(backing film)分离。JP-A-2002/241,725描述了包含硅烷改性的聚丙烯酸酯和附着到其上的填料微粒的水分散体。该分散体可用作压敏粘合剂。JP-A-2003/321,660公开了另外的压敏粘合剂,所述粘合剂包含含有硅烷改性的聚丙烯酸酯和氨基硅烷的水分散体。
另外,已经描述了使用包含聚合物组份和有机硅烷添加剂的粘合剂生产的层压物。US-A-2004/0092689描述了一种选定的丙烯酸类树脂,该树脂优选包含硅烷并且用于生产用于光学应用的层压物,例如用于生产LCD。EP-A-1,283,232公开了用于生产层压物的双组分粘合剂,所述粘合剂包含含有多异氰酸酯和硅烷偶联剂的固化剂组份和含有多元醇的基体组份。JP-A-11/245,346公开了包装用层压膜。该膜由具有非吸收性表面的两个膜构成,即层压到载体膜上的聚亚乙烯(polyvinylidine)。所使用的粘合剂是已添加有硅烷粘合促进剂的聚酯-聚氨酯树脂的水分散体。JP-A-09/125,039公开了用于木材-金属层压物的粘合剂。所述粘合剂包含水溶性聚合物或聚合物水分散体、填料、异氰酸酯交联剂和硅烷偶联剂。所述木材-金属层压物不可压纹。
DE 198 38 667 A1公开了选定的聚丙烯酸酯水分散体作为层压粘合剂的用途。在制备分散体的过程中,可以使用调节剂。在给定的实例中,调节剂是巯基丙基三甲氧基硅烷。
为了生产层压物,对层压粘合剂存在多种不同要求。例如,要求层压粘合剂应该适于将不同的材料例如聚合物膜、金属箔或金属化聚合物膜粘合到纸张和经涂布的纸和纸板上。层压粘合剂应该很好地粘合到所有上述基材上并且在层压之后应该在尽可能短的时间内在组件中产生高且持久的强度。还预期粘合剂即使在高速机器上也显示出无故障加工,这意味着即使用作粘合剂的分散体也必须显示出高的剪切稳定性和良好的流动性能。
在高光泽膜层压物的特定情况下,首先采用液体粘合剂涂布透明的聚合物膜。使粘合剂干燥,然后在热和压力下将粘合剂涂布的膜层压到基材(通常是印刷纸或印刷纸板)上。如此生产的层压物通常在层压之后另外加工相对短的时间,并将其压纹、折叠或开槽。上述情况引起的层压物的变形必须不伴随膜从基材上脱离的任一种情况。为了抑制上述情况的分离,通常使粘合剂层交联。这可通过向分散体中引入化学交联体系(如EP-A-148,386或EP-A-644,902中所述)、或通过添加水溶性异氰酸酯固化剂或通过引入UV交联基团(如DE-A-101 35 379中所述)进行。
考虑到化学交联粘合剂需要时间使其固化这一事实,采用上述体系在可以进一步处理层压体系之前必须等待一定的储存期。该缺点可通过使用UV固化粘合剂得以缓解。但是,这些体系使得在层压车间中需要外加辐射台,并且就可以使用的膜而言存在一定限制,因为不可以使用无光泽膜或对UV光不透明的膜。
基于上述现有技术,本发明的目的是提供一种层压物,所述层压物在不向层压车间引入外加设备的情况下在层压之后短时间内具有提高的压纹强度,而不损害层压物的其它性能。
现在已发现,可以通过添加有机硅烷将包含聚合物水分散体的粘合剂用于生产层压组件,所述层压组件显示出改进的可压纹性。
本发明提供了可压纹的层压物,所述层压物包含:
a)具有至少一个吸收性表面的片状基材,
b)膜,所述膜
c)通过粘合剂粘接到基材上,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷,该有机硅烷在聚合期间引入到聚合物中和/或随后添加并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团。
本发明的层压物必须可压纹,即,它们必须能够通过表面选定部分的适当压力处理而形成图案。本发明的层压物并非必须通过压纹形成图案。但是,优选所述层压物确实具有至少一个压纹表面。
本发明的层压物使用具有至少一个吸收性表面的片状基材生产。在本说明书中,所述基材是由纸张、纸板或其它纤维材料构成的挠性和刚性基材,实例是玻璃网、聚合物纤维网或天然纤维网。基材可由一种或多种材料构成或者本身可以是层压物,例如具有至少一个吸收性表面的聚合物层压物,如果需要所述层压物还可带有印刷电路。
特别优选使用片状并且同时是柔性和具有吸收性表面的基材。所述基材的实例是纸张,包括卡片和纸板,和其它纤维网。还可对这些材料进行印刷和/或涂布。
为了生产本发明的层压物,可以使用任何需要的膜。
象基材一样,这些膜可由各种材料,例如塑料、金属、胶合板或纸张构成。
优选金属或聚合物的膜,特别是透明聚合物膜。
优选使用的金属箔的实例是铝箔。
优选使用的聚合物膜的实例是聚乙烯(PE)、聚丙烯(PP),特别是取向聚丙烯(OPP)、聚苯乙烯(PS)、醋酸纤维素(CA)、聚氯乙烯(PVC)、聚酰胺(PA)和聚对苯二甲酸乙二醇酯(PET)的膜。
特别优选使用的透明聚合物膜的实例是取向(单轴或双轴取向)聚丙烯或醋酸纤维素的膜。
特别优选其中将基材表面印刷且聚合物膜是透明的的层压物。
另一种优选的层压物在膜一侧具有压纹。
根据本发明使用的粘合剂包含通过烯属不饱和单体的自由基乳液聚合制备的聚合物分散体。这种粘合剂本身是已知的。
适于制备聚合物分散体的烯属不饱和单体的选择本身并不重要。常规用于制备聚合物分散体的所有单体均是适合的,所述单体根据技术需要可合理地彼此结合。
优选的主要单体是具有1-18个碳原子的羧酸的乙烯基酯、烯属不饱和C3-C8一元羧酸和二羧酸与C1-C18烷基醇的全酯或单酯、和芳族或脂族烯属不饱和、任选卤代的烃。
作为具有1-8个碳原子的羧酸的乙烯基酯,可以使用本领域技术人员已知的所有单体。但是,特别优选具有1-4个碳原子的羧酸的乙烯基酯,例如甲酸乙烯酯、醋酸乙烯酯、丙酸乙烯酯、异丁酸乙烯酯、新戊酸乙烯酯和2-乙基己酸乙烯酯;酸基中具有9、10或11个碳原子的饱和支链一元羧酸(多能酸(Versatic acids))的乙烯基酯;长链饱和和不饱和脂肪酸的乙烯基酯,例如具有8-18个碳原子的脂肪酸的乙烯基酯,例如月桂酸乙烯酯和硬脂酸乙烯酯;苯甲酸或对叔丁基苯甲酸的乙烯基酯,及其混合物,例如醋酸乙烯酯和Versatic acid的混合物或醋酸乙烯酯和月桂酸乙烯酯的混合物。特别优选醋酸乙烯酯。
作为烯属不饱和C3-C8一元羧酸和二羧酸与C1-C18烷基醇的全酯或单酯,可以使用本领域技术人员已知的所有单体。此处优选烯属不饱和C3-C8一元羧酸和二羧酸与C1-C12烷基醇,且特别优选C1-C8烷基醇或C5-C8环烷基醇的全酯或单酯。适合的C1-C18烷基醇的实例是甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇、叔丁醇、正己醇、2-乙基己醇、月桂醇和硬脂醇。适合的环烷基醇的实例是环戊醇和环己醇。
特别优选丙烯酸、甲基丙烯酸、巴豆酸、马来酸、衣康酸、柠康酸和富马酸的酯。特别优选丙烯酸和/或甲基丙烯酸的酯,例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸1-己基酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯,和富马酸和马来酸的酯,例如富马酸二甲酯、马来酸二甲酯、马来酸二正丁酯、马来酸二正辛酯和马来酸二(2-乙基己基)酯。适当的情况下,所述酯还可由环氧基和/或羟基所取代。
芳族或脂族烯属不饱和、任选卤代的烃的实例是乙烯、丙烯、1-丁烯、2-丁烯、异丁烯、苯乙烯、乙烯基甲苯、氯乙烯和偏二氯乙烯,优选乙烯和苯乙烯。
除了上述主要的单体,可以使用官能单体。这些单体包括具有官能团的离子单体和非离子单体。
离子单体包括紧邻双键单元带有至少一个羧酸基、磺酸基、磷酸基或膦酸基或经间隔基连接到所述单元的那些化合物。可以提及的实例包括如下物质:烯属不饱和C3-C8一元羧酸、烯属不饱和C5-C8二羧酸及其酸酐和烯属不饱和C4-C8二羧酸的单酯。
优选烯属不饱和一元羧酸,例如丙烯酸和甲基丙烯酸以及其酸酐;不饱和二羧酸,例如马来酸、富马酸、衣康酸和柠康酸以及其与C1-C12烷基醇的单酯,例如马来酸单甲酯和马来酸单正丁酯。其它优选的烯属不饱和离子单体是烯属不饱和磺酸例如乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸、2-丙烯酰氧基乙磺酸和2-甲基丙烯酰氧基乙磺酸、3-丙烯酰氧基丙磺酸和3-甲基丙烯酰氧基丙磺酸、乙烯基苯磺酸,和烯属不饱和膦酸,例如乙烯基膦酸。
另外,如上所述,还可以使用其盐,优选其碱金属盐或铵盐,且更优选其钠盐,例如乙烯基磺酸和2-丙烯酰胺基丙磺酸的钠盐。
另外适合的烯属不饱和离子单体包括具有阳离子官能团的单体,例如基于例如季铵基的单体。但是,优选阴离子单体。
烯属不饱和非离子官能单体包括,例如针对烯属不饱和离子单体规定的羧酸的酰胺,例如甲基丙烯酰胺和丙烯酰胺,和水溶性N-乙烯基内酰胺,例如N-乙烯基吡咯烷酮,和含有共价键合的聚乙二醇单元作为烯属不饱和化合物的化合物,例如聚乙二醇单烯丙基醚或二烯丙基醚或烯属不饱和羧酸与聚亚烷基二醇的酯。
此外,另外适合的烯属不饱和非离子官能单体是烯属不饱和C3-C8羧酸的腈,例如丙烯腈和甲基丙烯腈,以及促进粘合和交联用单体。还可以使用C4-C8共轭二烯,例如1,3-丁二烯、异戊二烯和氯丁二烯作为单体。
促进粘合用单体不仅包括具有共价连接到双键体系的乙酰乙酰氧基单元的化合物而且包括含有共价键合的脲基的化合物。特别地,首先提及的化合物包括(甲基)丙烯酸乙酰乙酰氧基乙基酯和乙酰乙酸烯丙酯。含有脲基的化合物包括,例如N-乙烯基脲和N-烯丙基脲以及咪唑啉-2-酮的衍生物,例如N-乙烯基咪唑烷-2-酮和N-烯丙基咪唑烷-2-酮、N-乙烯氧基乙基咪唑烷-2-酮、N-(2-(甲基)丙烯酰胺基乙基)咪唑烷-2-酮、N-(2-(甲基)丙烯酰氧基乙基)咪唑烷-2-酮、N-(2-(甲基)丙烯酰氧基乙酰胺基乙基)咪唑烷-2-酮和另外的粘合促进剂,所述另外的粘合促进剂是技术人员已知的并且基于脲或咪唑烷-2-酮。还适于提高粘合性的是结合随后向分散体中添加己二酰肼的二丙酮丙烯酰胺。
作为交联用单体,不仅可以使用双官能单体,而且可以使用多官能单体。其实例是邻苯二甲酸二烯丙酯、马来酸二烯丙酯、氰尿酸三烯丙酯、四烯丙氧基乙烷、二乙烯基苯、二(甲基)丙烯酸丁-1,4-二醇酯、二(甲基)丙烯酸三甘醇酯、己二酸二乙烯酯、(甲基)丙烯酸烯丙酯、巴豆酸乙烯酯、亚甲基二丙烯酰胺、己二醇二丙烯酸酯、季戊四醇二丙烯酸酯和三羟甲基三丙烯酸酯。
适当的情况下,官能单体可以基于单体总量,以0.1重量%-25重量%,优选0.5重量%-10重量%的量使用。适当的情况下,交联用单体可以基于单体总量,0.02重量%-5重量%,优选0.02重量%-1重量%的量使用。
当选择适当的单体或单体组合物时,必须考虑通常公认与制备分散体有关的前景,所述分散体用于制备粘合剂。因此,必须特别确保形成在用于涂层的预定干燥条件下形成粘合剂膜的聚合物,和对制备共聚物的单体进行选择以便根据聚合参数的状况可形成共聚物。
优选使用衍生自丙烯酸酯、甲基丙烯酸酯和/或脂族羧酸的乙烯基酯的聚合物分散体。
适当的情况下与乙烯基酯一起用于制备聚(甲基)丙烯酸酯的单体的优选单体混合物是醋酸乙烯酯/丙烯酸丁酯、醋酸乙烯酯/马来酸二丁酯、醋酸乙烯酯/富马酸二丁酯、醋酸乙烯酯/丙烯酸2-乙基己酯、醋酸乙烯酯/乙烯/丙烯酸丁酯、醋酸乙烯酯/乙烯/马来酸二丁酯、醋酸乙烯酯/乙烯/富马酸二丁酯、醋酸乙烯酯/乙烯/丙烯酸2-乙基己酯、甲基丙烯酸甲酯/丙烯酸丁酯、甲基丙烯酸甲酯/丙烯酸2-乙基己酯、苯乙烯/丙烯酸丁酯、苯乙烯/丙烯酸2-乙基己酯、甲基丙烯酸甲酯/丙烯酸异丁酯和甲基丙烯酸甲酯/丙烯酸异丙酯。
在适当的情况下与另外的官能单体一起用于制备聚乙烯基酯的单体的另外优选的单体混合物是醋酸乙烯酯/氯乙烯/乙烯、醋酸乙烯酯/月桂酸乙烯酯/乙烯、醋酸乙烯酯/月桂酸乙烯酯/乙烯/氯乙烯、醋酸乙烯酯/Versatic酸乙烯酯/乙烯/氯乙烯、Versatic酸乙烯酯/乙烯/氯乙烯、醋酸乙烯酯/Versatic酸乙烯酯/乙烯和醋酸乙烯酯/乙烯,特别优选醋酸乙烯酯/乙烯的组合。
特别优选所使用的粘合剂是通过自由基乳液聚合制备的聚合物分散体,所述聚合物分散体是衍生自丙烯酸酯和/或甲基丙烯酸酯作为主要单体的均聚物或共聚物(“聚丙烯酸酯”)或者是衍生自乙烯基酯作为主要单体的均聚物或共聚物(“聚乙烯基酯”),优选玻璃化转变温度低于15℃的聚丙烯酸酯或聚乙烯基酯。聚合物的玻璃化转变温度可由技术人员经过单体组合物的适当选择调节。
根据本发明使用的分散体通过保护胶体和/或乳化剂稳定。
保护胶体是分子量例如大于2000g/mol的聚合物,而乳化剂是相对分子量例如低于2000g/mol的低分子量化合物。这些化合物在实际聚合过程中加入并且适当的情况下还可在聚合之后再次加入。
保护胶体的实例是淀粉、阿拉伯树胶、藻脘酸盐或黄蓍胶、甲基纤维素、乙基纤维素、羟乙基纤维素或羧甲基纤维素、或采用饱和酸或环氧化物改性的淀粉、以及合成物质例如聚乙烯醇(存在或不存在残余量的乙酰基)或采用饱和基团部分酯化、缩醛化或醚化的聚乙烯醇、和多肽,例如明胶,以及聚乙烯吡咯烷酮、聚乙烯基甲基乙酰胺或聚(甲基)丙烯酸。优选聚乙烯醇。
当存在时,基于制备所用单体的总量,所述保护胶体的重量分数通常最高15%。
另外,在许多情况下有利的是除了保护胶体以外或者代替保护胶体,在制备分散体的过程中使用非离子和/或离子乳化剂。
适合的非离子乳化剂是芳脂族和脂族非离子乳化剂,例如乙氧基化单、二和三烷基酚(EO度:3-50,烷基:C4-C9)、长链醇的乙氧基化物(EO度:3-50,烷基:C8-C36)以及聚氧化乙烯/聚氧化丙烯嵌段共聚物。优选使用长链醇的乙氧基化物(烷基:C10-C22,平均乙氧基化度:3-50)和,其中,特别优选具有线形或支化的C12-C18烷基且乙氧基化度为8-50的基于氧化的醇、天然存在的醇或Guerbet醇的乙氧基化物。
另外适合的乳化剂见于,例如Houben-Weyl,Methoden derorganischen Chemie[有机化学方法],第XIV/1卷,MacromolekulareStoffe[大分子化合物],Georg-Thieme-Verlag,Stuttgart,1961,第192-208页中。
适合的离子乳化剂包括阴离子和阳离子乳化剂。
阴离子乳化剂包括硫酸烷基酯(烷基:C8-C18)、膦酸烷基酯(烷基:C8-C18)的碱金属盐和铵盐,乙氧基化烷基醇(EO度:2-50,烷基:C8-C22)和乙氧基化烷基酚(EO度:3-50,烷基C4-C9)的硫酸单酯或磷酸单酯和二酯的碱金属盐和铵盐,烷基磺酸(烷基:C12-C18)的碱金属盐和铵盐,烷基芳基磺酸(烷基:C9-C18)的碱金属盐和铵盐,烷基醇(烷基:C8-C22)和乙氧基化烷基醇(EO度:2-50,烷基:C8-C22)以及非乙氧基化和乙氧基化烷基酚(EO度:3-50,烷基:C4-C9)的磺基琥珀酸单酯和磺基琥珀酸二酯的碱金属盐和铵盐。通常,将所列乳化剂作为工业混合物使用。烷基长度和EO链长的论述指的是混合物中存在的相应分布的最大值。所述种类的乳化剂的实例是Texapon K12(购自Cognis的月桂基硫酸钠)、Emulsogen EP(购自Clariant的C13-C17烷基磺酸盐)、Maranil A 25 IS(购自Cognis的正烷基(C10-C13)苯磺酸钠)、Genapol ZRO(购自Clariant的具有3个EO单元的C12/C14烷基醚硫酸钠)、Hostapal BVQ-4(具有4个EO单元的壬基酚醚硫酸钠,购自Clariant)、Aerosol MA 80(购自CytecIndustries的二己基磺基琥珀酸钠)、Aerosol A-268(购自Cytec Industries的异癸基磺基琥珀酸二钠)和Aerosol A-103(乙氧基化壬基酚的磺基琥珀酸单酯的二钠盐,购自Cytec Industries)。
阳离子乳化剂包括,例如乙酸烷基铵(烷基:C8-C12)、含有铵基的季铵化合物和吡啶盐化合物。
关于离子乳化剂的选择,当然必须确保消除所得到的聚合物分散体中的不相容性(上述不相容性可能导致絮凝)。因此,优选使用阴离子乳化剂与阴离子单体相结合或者使用阳离子乳化剂与阳离子单体相结合,特别优选阴离子乳化剂与阴离子单体相结合。
使用的情况下,乳化剂的用量在通常可见的界限内。总的来说,因此使用最高达约10重量%,优选最高达5重量%,基于制备分散体所用单体的总量。通常,使用离子和非离子乳化剂的混合物,尽管为了另外使分散体稳定还可以单独使用离子和非离子乳化剂。
根据本发明使用的聚合物水分散体通常具有的固含量为20重量%-70重量%,优选30重量%-65重量%,且更优选40重量%-60重量%。
如果需要,根据本发明使用的聚合物分散体另外包含本身通用的额外的助剂。
可以使用的添加剂和另外的成分包括成膜助剂,例如石油溶剂、Texanol、TxiB、丁二醇、丁基二乙二醇(butyl diglycol)、丁基二丙二醇、和丁基三丙二醇;增塑剂,例如邻苯二甲酸二甲酯、邻苯二甲酸二异丁酯、己二酸二异丁酯、Coasol B和Plastilit 3060;润湿剂,例如AMP 90、TegoWet.280、Fluowet PE;增稠剂,例如聚丙烯酸酯或聚氨酯,例如Borchigel L75和Tafigel PUR 60;消泡剂,实例是矿物油消泡剂或硅油消泡剂;UV稳定剂,Tinuvin 1130、后添加(retro-added)的稳定乳化剂或聚合物,例如聚乙烯醇或纤维素醚、流变改性剂,实例是聚丙烯酸酯或聚氨酯增稠剂,以及在粘合剂的制剂中也通用的其它的添加剂和助剂。
根据本发明使用的粘合剂的最小成膜温度通常低于25℃,优选低于15℃。成膜温度可通过添加常规聚结剂改进和调节。
根据本发明使用的聚合物分散体通过自由基乳液聚合制备。其可通过间歇工艺、进料工艺、组合的间歇/进料工艺或连续工艺进行。
但是,优选以组合的间歇/进料工艺的方式操作或者,特别优选以进料工艺的方式操作,其中通常在开始时将部分单体(1重量%-15重量%)加入以引发聚合。单体的计量可一起或以单独进料的方式进行。另外在某些实施方案中有利的是进行种子聚合以便设定特定的粒度和粒度分布。
所用自由基引发剂的实例包括如下物质:过氧化氢、过氧化苯甲酰、环己酮过氧化物、异丙基枯基氢过氧化物、钾、钠和铵的过硫酸盐、链长为C8-C12的偶数饱和的单价脂族羧酸的过氧化物、叔丁基氢过氧化物、二叔丁基过氧化物、过碳酸二异丙酯、偶氮二异丁腈、乙酰环己磺酰基过氧化物、过苯甲酸叔丁酯、过辛酸叔丁酯、二-3,5,5-三甲基己酰基过氧化物、过新戊酸叔丁酯、氢过氧化蒎烷和萜烷氢过氧化物。前述化合物还可作为氧化还原体系的一部分使用,所述氧化还原体系包括过渡金属盐例如铁(II)盐或其它还原剂。作为还原剂或调节剂,可以使用氧化甲烷亚磺酸的碱金属盐、C10-C14链长的硫醇、丁-1-烯-3-醇、羟基胺盐、二烷基二硫代氨基甲酸钠、亚硫酸氢钠、亚硫酸氢铵、连二亚硫酸钠、二异丙基黄原素二硫化物、抗坏血酸、酒石酸、异抗坏血酸、硼酸、脲和甲酸。
但是,优选使用水溶性过硫酸盐,特别是过硫酸铵或过硫酸钠引发聚合。
用于稳定化的乳化剂和/或保护胶体同样可择一地在聚合开始时全部包含在初始进料中、或部分包含在初始进料中、部分计量加入,或者全部在聚合过程中计量加入。
分散体的pH通常为2-7,优选2.5-6。
聚合温度通常为20-120℃,优选30-110℃,且特别优选45-95℃。
聚合之后,为了脱单体可以进行进一步后处理,再优选进行化学后处理,特别是使用氧化还原催化剂,例如前述氧化剂和还原剂的组合物。此外,可以通过已知方法,例如通过物理脱单体,即蒸馏脱除(特别是经蒸汽蒸馏)或通过采用惰性气体汽提除去存在的残余单体。物理和化学方法相结合特别有效并且能将残余单体降低至很低水平(<1000ppm,优选<100ppm)。
根据本发明使用的粘合剂中的聚合物的用量通常为55重量%-99.9重量%,优选80-99.8重量%,基于粘合剂的固含量。
根据本发明使用的粘合剂包含至少一种有机硅烷。所述硅烷可在实际制备聚合物分散体的过程中存在和/或可以随后加入。有机硅烷化合物的用量通常为0.05重量%-20重量%,优选0.05重量%-5重量%,基于粘合剂的固含量。
可以使用任一种有机硅烷,所述有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者其包含烯属不饱和基团和硅烷基团。可能的化合物是在聚合过程中结合入聚合物中的那些化合物和在分散体中与聚合物一起作为独立的组份存在的那些化合物。
根据本发明使用的有机硅烷优选包括式I或II的化合物
a)有机官能硅烷
其中R1为-(CH2)n-NH-R4、-(CH2)n-NH-[(CH2)m-NH]o-R4、-(CH2)n-O-R5或-(CH2)1-CH=CH2,
R2为氢、-(CH2)n-CH3或R1,
R3为氢、-(CH2)n-CH3或R2,
R4为氢、-(CH2)n-CH3或-CO-(CH2)m-CH3,和
R5为氢、-(CH2-CH2-O)m-R4或
n和m彼此独立各为0-12的整数,且o为0-5的整数。
另外优选使用的硅烷是多官能硅烷。具体地说,它们包括除了至少一个硅烷基团还具有至少一个伯、仲或叔氨基或至少一个环氧基的化合物,或者分子中含有两个或多个烯属不饱和基团的多官能硅烷。
在上述化合物中特别优选的化合物是式III、IV、V或VI的化合物
(R6-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-R6)3 (III)
(R6-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-R6]2 (IV)
(R6-O)3-Si-(CH2)p-O-R7 (V)
(R6-O)3-Si-(CH2)p-NR8R9 (VI)
其中R6在每种情况下独立地为氢或C1-C6烷基,优选甲基、乙基或丙基,
R7为缩水甘油基(1,2-环氧丙基),
R8和R9彼此独立地为氢或C1-C6烷基,和
p为1-12的整数。
式III和IV的特别优选的硅烷是如下化合物:
(CH3-CH2-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-CH2-CH3)3,
(CH3-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-CH3)3,
(CH3-CH2-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-CH2-CH3)3]2,
(CH3-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-CH3)3]2,
其中p如上定义。
硅烷可作为单独的化合物或作为混合物使用。
可商购的前述类型的硅烷化合物的可提及实例包括如下化合物:商品名Dynasylan(Degussa)的硅烷、商品名ADDID或Geniosil(Wacker)的硅烷或商品名Silquest(Crompton)的硅烷。
可加入到聚合物中的有机硅烷包括烯属不饱和单体,所述单体包含硅烷基团并且符合式R11Si(CH3)0-2(OR12)3-1,其中R11具有定义CH2=CR13-(CH2)0-1或CH2=CR13CO2-(CH2)1-3,R12是具有1-12个碳原子的非支化或支化、非取代或取代的烷基并且可以不插入或插入醚基中断,且R13为氢或甲基。
优选的硅烷符合式CH2=CR13-(CH2)0-1Si(CH3)0-1(OR12)3-2和CH2=CR13CO2-(CH2)3Si(CH3)0-1(OR12)3-2,其中R12是具有1-12个碳原子的非支化或支化、非取代或取代的烷基并且R13为氢或甲基。
特别优选的硅烷是乙烯基甲基二甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基甲基二正丙氧基硅烷、乙烯基甲基二异丙氧基硅烷、乙烯基甲基二正丁氧基硅烷、乙烯基甲基二仲丁氧基硅烷、乙烯基甲基二叔丁氧基硅烷、乙烯基甲基二(2-甲氧基异丙氧基)硅烷和乙烯基甲基二辛氧基硅烷。
尤其优选的硅烷符合式CH2=CR13-(CH2)0-1Si(OR14)3和CH2=CR13CO2-(CH2)3Si(OR14)3,其中R14是具有1-4个碳原子的支化或非支化的烷基并且R13为氢或甲基。
其实例是γ-(甲基)丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、γ-(甲基)丙烯酰氧基丙基三甲氧基硅烷、γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三正丙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三异丙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三丁氧基硅烷、γ-(甲基)丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、γ-丙烯酰氧基丙基三甲氧基硅烷、γ-丙烯酰氧基丙基三乙氧基硅烷、γ-丙烯酰氧基丙基三正丙氧基硅烷、γ-丙烯酰氧基丙基三异丙氧基硅烷、γ-丙烯酰氧基丙基三丁氧基硅烷和乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三正丙氧基硅烷、乙烯基三异丙氧基硅烷和乙烯基三丁氧基硅烷。适当的情况下所述硅烷化合物还可以其(部分)水解产物的形式使用。
特别优选使用的硅烷是伯和仲氨基烷基乙氧基硅烷、二(3-三乙氧基甲硅烷基丙基)胺、三官能丙基三甲氧基硅烷[NH2-(CH2)2-NH-(CH2)2-NH-(CH2)3-Si(OCH3)3]、乙烯基三乙氧基硅烷[CH2=CH-Si(OC2H5)3]、乙烯基三甲氧基硅烷[CH2=CH-Si(OCH3)3]、3-缩水甘油氧基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、低聚二氨基硅烷体系、缩水甘油基-三甲氧基-官能硅烷、乙烯基-三乙氧基-官能硅烷、缩水甘油基-三乙氧基-官能硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、(3-缩水甘油氧基丙基)三甲氧基硅烷、N-(2-氨基乙基)(3-氨基丙基)三甲氧基硅烷、(3-氨基丙基)三乙氧基硅烷、N-(2-氨基乙基)(3-氨基丙基)甲基二甲氧基硅烷、(3-氨基丙基)三甲氧基硅烷、(甲基丙烯酰氧基甲基)甲基二甲氧基硅烷、(甲基丙烯酰氧基甲基)三甲氧基硅烷和/或(甲基丙烯酰氧基甲基)甲基二乙氧基硅烷。
在根据本发明使用的粘合剂中,有机硅烷通常以基于粘合剂的固含量,0.001重量%-20重量%的量存在。优选有机硅烷以0.001重量%-10重量%的量使用。
众所周知,硅烷化合物还用于提高粘合性。但是,提高粘合性并不一定产生与生产层压物有关的在压纹强度方面的改进。
为了改进聚合物分散体与硅烷化合物之间的相容性,必须在添加有机官能硅烷之前通过添加表面活性剂或保护胶体使聚合物分散体稳定化。
本发明还提供了一种生产上述层压物的方法,该方法包括如下步骤:
i)采用粘合剂涂布基材的至少一个吸收性表面,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷,该有机硅烷在聚合过程中结合到聚合物中和/或随后加入并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团,
ii)采用常规方法将膜层压到粘合剂涂布的表面上,和
iii)如果需要,将层压物压到层压膜的一侧。
本发明的层压物可例如用于生产包装纸板盒和其它包装材料、书脊、小册子、广告媒介、明信片、训练板(training board)和身份证和芯片卡。上述用途也由本发明提供。
本发明另外提供了包含有机硅烷和通过自由基乳液聚合制备的聚合物分散体的粘合剂用于将聚合物膜粘合到多孔基材上和用于高光泽膜的层压的用途。
以下实施例阐明本发明而不是对其进行限制。
实施例1:
将玻璃化转变温度Tg为-18℃的基于甲基丙烯酸甲酯和丙烯酸2-乙基己酯的丙烯酸酯共聚物的水分散体与0.5%的乳化剂(Emulsogen EPN 287)和0.5%的氨基硅烷(N-(2-氨基乙基)(3-氨基丙基)三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(Brookfield RVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
层压在层压设备上进行,其中通过喷枪将粘合剂施涂到OPP膜的预处理一侧。施涂粘合剂之后,使膜通过在温度为60-70℃下操作的干燥通道。在干燥通道之后通过硅树脂辊与加热至80℃的辊之间在热激活的情况下进行膜和印刷载体的层压。
在一部分层压样品上采用直接比较的方式在80℃下进行剥离强度和热稳定性的测定。在所有情况下针对不同的剥离速率将剥离强度的结果记录为三次测量的平均值,以N/2.5cm计。热稳定性的结果记录为在载荷为在100g或200g下在样品2.5cm宽取样上于80℃下达到5cm剥离长度之后的时间。此处,所记录数字也为三次单独测量的平均值。
在辊式压纹设备中将第二部分层压样品在层压之后24h进行压纹测试(亚麻图案),压力设定在使在压纹边缘处不再存在纸张纤维的起绒(raising)的水平下。评价压纹之后24小时是否存在可见的分层标志-例如呈灰色。所述测试总采用直接比较的方式进行。
表1:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 9.4 | 2.1 | 2.2 | 2.4 | 2.8 | 2.9 | 1∶47 | 0∶11 | 明显分层 |
有硅烷 | 8.3 | 2.4 | 2.4 | 2.7 | 2.9 | 3.2 | 2∶27 | 0∶19 | 稍微分层 |
实施例2:
将玻璃化转变温度Tg为-18℃的基于甲基丙烯酸甲酯和丙烯酸2-乙基己酯的丙烯酸酯共聚物的水分散体与1%的环氧化硅烷(γ-缩水甘油氧基丙基三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(Brookfield RVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
采用如实施例1相同的方式进行层压和层压样品的性能测定。结果列于表2中。
表2:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 9.4 | 2.1 | 2.2 | 2.4 | 2.8 | 2.9 | 1∶47 | 0∶11 | 明显分层 |
有硅烷 | 10.3 | 2.7 | 2.6 | 2.7 | 2.9 | 3.1 | 3∶24 | 0∶38 | 几乎无分层 |
实施例3:
将玻璃化转变温度Tg为-20℃的基于甲基丙烯酸甲酯和丙烯酸丁酯的丙烯酸酯共聚物的水分散体与0.5%的环氧化硅烷(γ-缩水甘油氧基丙基三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(Brookfield RVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
采用如实施例1相同的方式进行层压和层压样品的性能测定。结果列于表3中。
表3:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 10.2 | 3.7 | 3.5 | 3.7 | 4.3 | 4.6 | 20∶34 | 1∶08 | 明显分层 |
有硅烷 | 10.3 | 3.3 | 3.3 | 3.3 | 4.2 | 4.0 | 4∶14 | 0∶24 | 无分层 |
实施例4:
将基于甲基丙烯酸甲酯和丙烯酸丁酯的丙烯酸酯共聚物(AcronalA310)的水分散体与1%的环氧化硅烷(γ-缩水甘油氧基丙基三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(Brookfield RVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
采用如实施例1相同的方式进行层压和层压样品的性能测定。结果列于表4中。
表4:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 10.4 | 4.6 | 4.6 | 4.9 | 5.5 | 6.3 | 15∶22 | 1∶42 | 明显分层 |
有硅烷 | 10.3 | 3.5 | 3.5 | 3.4 | 4.2 | 4.6 | 8∶00 | 1∶09 | 无分层 |
实施例5:
将阴离子稳定化的具有25%甲基丙烯酸甲酯和75%丙烯酸丁酯作为主要单体的粉末共聚物分散体(固含量:50.5%,pH:8.2,Tg:-21℃,粒度分布:Mastersizer,多峰Mie评价:dn=220nm,dw=260nm)与1%的氨基硅烷(N-(2-氨基乙基)(3-氨基丙基)三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(Brookfield RVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
采用如实施例1相同的方式进行层压和层压样品的性能测定。结果列于表5中。
表5:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 9.5 | 2.4 | 2.5 | 2.7 | 3.0 | 3.2 | 1∶35 | 0∶10 | 明显分层 |
有硅烷 | 10.2 | 3.0 | 2.6 | 2.7 | 3.2 | 3.6 | 5∶35 | 0∶17 | 几乎无分层 |
实施例6:
将阴离子稳定化的具有30%甲基丙烯酸甲酯和70%丙烯酸2-乙基己酯作为主要单体的粉末共聚物分散体(固含量:52.3%,pH:8.0,Tg:-18℃,粒度分布:Mastersizer,多峰Mie评价:dn=190nm,dw=200nm)与1%的环氧化硅烷(γ-缩水甘油氧基丙基三甲氧基硅烷)混合。在采用水稀释之后将初始分散体和混合物各自调节至粘度为约100mPa*s(BrookfieldRVT,转子1/20rpm,23℃)并用于将OPP膜(20μm厚,在一侧上电晕预处理;Trespaphan NND 20)层压到深黑印刷的纸板(100g/m2)上。
采用如实施例1相同的方式进行层压和层压样品的性能测定。结果列于表6中。
表6:层压测试的结果
所用的层压粘合剂 | 粘合剂施涂速率(g/m2) | 在一定剥离速率下层压物的剥离强度,以N/2.5cm计 | 80℃下的热稳定性,以分钟计 | 压纹评价 | |||||
5cm/min | 10cm/min | 20cm/min | 40cm/min | 60cm/min | 100g/2.5cm | 200g/2.5cm | |||
无硅烷 | 10.7 | 2.9 | 3.1 | 3.4 | 3.7 | 3.9 | 18∶38 | 1∶00 | 明显分层 |
有硅烷 | 9.5 | 3.3 | 3.2 | 4.1 | 3.4 | 3.9 | 3∶51 | 0∶29 | 无分层 |
Claims (22)
1、可压纹层压物,所述层压物包括:
a)具有至少一个吸收性表面的片状基材,
b)膜,所述膜
c)通过粘合剂粘接到基材上,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷,该有机硅烷在聚合期间引入到聚合物中和/或随后加入并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团。
2、权利要求1的层压物,其中所述基材选自纸张、卡片、纸板和其它纤维网。
3、权利要求2的层压物,其中将基材印刷和/或涂布。
4、权利要求1的层压物,其中膜选自金属箔或聚合物膜。
5、权利要求4的层压物,其中将基材印刷并且其中聚合物膜是透光的。
6、权利要求1的层压物,其中通过自由基乳液聚合制备的聚合物分散体是聚丙烯酸酯或聚乙烯基酯,优选玻璃化转变温度低于15℃的聚丙烯酸酯或聚乙烯基酯。
7、权利要求1的层压物,其中通过自由基乳液聚合制备的聚合物分散体衍生自主要单体醋酸乙烯酯/丙烯酸丁酯、醋酸乙烯酯/马来酸二丁酯、醋酸乙烯酯/富马酸二丁酯、醋酸乙烯酯/丙烯酸2-乙基己酯、醋酸乙烯酯/乙烯/丙烯酸丁酯、醋酸乙烯酯/乙烯/马来酸二丁酯、醋酸乙烯酯/乙烯/富马酸二丁酯、醋酸乙烯酯/乙烯/丙烯酸2-乙基己酯、甲基丙烯酸甲酯/丙烯酸丁酯、甲基丙烯酸甲酯/丙烯酸2-乙基己酯、苯乙烯/丙烯酸丁酯、苯乙烯/丙烯酸2-乙基己酯、甲基丙烯酸甲酯/丙烯酸异丁酯或甲基丙烯酸甲酯/丙烯酸异丙酯。
8、权利要求1的层压物,其中通过自由基乳液聚合制备的聚合物分散体衍生自主要单体醋酸乙烯酯/氯乙烯/乙烯、醋酸乙烯酯/月桂酸乙烯酯/乙烯、醋酸乙烯酯/月桂酸乙烯酯/乙烯/氯乙烯、醋酸乙烯酯/Versatic酸乙烯酯/乙烯/氯乙烯、Versatic酸乙烯酯/乙烯/氯乙烯、醋酸乙烯酯/Versatic酸乙烯酯/乙烯和醋酸乙烯酯/乙烯,特别优选醋酸乙烯酯/乙烯的组合。
10、权利要求1的层压物,其中所述有机硅烷是除了至少一个硅烷基团还具有至少一个伯、仲或叔氨基或至少一个环氧基的化合物。
11、权利要求10的层压物,其中所述有机硅烷是式III、IV、V或VI的化合物
(R6-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-R6)3 (III),
(R6-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-R6)3]2 (IV),
(R6-O)3-Si-(CH2)p-O-R7 (V),
(R6-O)3-Si-(CH2)p-NR8R9 (VI),
其中R6在每种情况下独立地为氢或C1-C6烷基,优选甲基、乙基或丙基,
R7为缩水甘油基(1,2-环氧丙基),
R8和R9彼此独立地为氢或C1-C6烷,和
p为1-12的整数。
12、权利要求11的层压物,其中所述有机硅烷是下式的化合物
(CH3-CH2-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-CH2-CH3)3,
(CH3-O)3-Si-(CH2)p-NH-(CH2)p-Si-(O-CH3)3,
(CH3-CH2-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-CH2-CH3)3]2和/或
(CH3-O)3-Si-(CH2)p-N[-(CH2)p-Si-(O-CH3)3]2,
其中p如权利要求11中所定义。
13、权利要求1的层压物,其中所述有机硅烷是含有硅烷基团的烯属不饱和化合物并且符合式R11Si(CH3)0-2(OR12)3-1,其中R11符合式CH2=CR13-(CH2)0-1或CH2=CR13CO2-(CH2)1-3,R12是具有1-12个碳原子的非支化或支化、非取代或取代的烷基并且可以不插入或插入醚基,且R13为氢或甲基。
14、权利要求1的层压物,其中所述有机硅烷是含有硅烷基团的烯属不饱和化合物并且符合式CH2=CR13-(CH2)0-1Si(CH3)0-1(OR12)3-2和CH2=CR13CO2-(CH2)3Si(CH3)0-1(OR12)3-2,其中R12是具有1-12个碳原子的非支化或支化、非取代或取代的烷基并且R13为氢或甲基。
15、权利要求14的层压物,其中所述有机硅烷是选自乙烯基甲基二甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基甲基二正丙氧基硅烷、乙烯基甲基二异丙氧基硅烷、乙烯基甲基二正丁氧基硅烷、乙烯基甲基二仲丁氧基硅烷、乙烯基甲基二叔丁氧基硅烷、乙烯基甲基二(2-甲氧基异丙氧基)硅烷和/或乙烯基甲基二辛氧基硅烷的化合物。
16、权利要求14的层压物,其中所述有机硅烷是式CH2=CR13-(CH2)0-1Si(OR14)3和CH2=CR13CO2-(CH2)3Si(OR14)3的化合物,其中R14是具有1-4个碳原子的支化或非支化的烷基并且R13为氢或甲基。
17、权利要求16的层压物,其中所述有机硅烷是选自γ-(甲基)丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、γ-(甲基)丙烯酰氧基丙基三甲氧基硅烷、γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三正丙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三异丙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三丁氧基硅烷、γ-(甲基)丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、γ-丙烯酰氧基丙基三甲氧基硅烷、γ-丙烯酰氧基丙基三乙氧基硅烷、γ-丙烯酰氧基丙基三正丙氧基硅烷、γ-丙烯酰氧基丙基三异丙氧基硅烷、γ-丙烯酰氧基丙基三丁氧基硅烷和乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三正丙氧基硅烷、乙烯基三异丙氧基硅烷和/或乙烯基三丁氧基硅烷的化合物。
18、权利要求1的层压物,其中有机硅烷是选自伯和仲氨基烷基乙氧基硅烷、二(3-三乙氧基甲硅烷基丙基)胺、三官能丙基三甲氧基硅烷[NH2-(CH2)2-NH-(CH2)2-NH-(CH2)3-Si(OCH3)3]、乙烯基三乙氧基硅烷[CH2=CH-Si(OC2H5)3]、乙烯基三甲氧基硅烷[CH2=CH-Si(OCH3)3]、3-缩水甘油氧基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、低聚二氨基硅烷体系、缩水甘油基-三甲氧基-官能硅烷、乙烯基-三乙氧基-官能硅烷、缩水甘油基-三乙氧基-官能硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、(3-缩水甘油氧基丙基)三甲氧基硅烷、N-(2-氨基乙基)(3-氨基丙基)三甲氧基硅烷、(3-氨基丙基)三乙氧基硅烷、N-(2-氨基乙基)(3-氨基丙基)甲基二甲氧基硅烷、(3-氨基丙基)三甲氧基硅烷、(甲基丙烯酰氧基甲基)甲基二甲氧基硅烷、(甲基丙烯酰氧基甲基)三甲氧基硅烷和/或(甲基丙烯酰氧基甲基)甲基二乙氧基硅烷的化合物。
19、权利要求1的层压物,其在膜一侧具有压纹。
20、生产权利要求1的层压物的方法,该方法包括如下步骤:
i)采用粘合剂涂布基材的至少一个吸收性表面,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷,该有机硅烷在聚合过程中引入聚合物中和/或随后加入并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团,
ii)采用常规方法将膜层压到粘合剂涂布的表面上,和
iii)如果需要,将层压物压到层压膜的一侧。
21、权利要求1的层压物的用途,用于生产包装纸板盒、其它包装材料、书脊、小册子、广告媒介、明信片、训练板、身份证或芯片卡。
22、粘合剂的用途,用于将聚合物膜粘合到多孔基材上和用于高光泽膜的层压,所述粘合剂包含通过自由基乳液聚合制备的聚合物分散体和有机硅烷,该有机硅烷在聚合过程中引入聚合物中和/或随后加入并且该有机硅烷除了至少一个硅烷基团以外还具有至少一个伯、仲或叔氨基或至少一个环氧基或者该有机硅烷包含至少一个烯属不饱和基团和至少一个硅烷基团。
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2005
- 2005-05-13 DE DE102005022166A patent/DE102005022166A1/de not_active Withdrawn
-
2006
- 2006-03-30 EP EP06006660A patent/EP1721731A1/de not_active Withdrawn
- 2006-05-12 CN CNA2006100802313A patent/CN1864989A/zh active Pending
- 2006-05-13 US US11/433,860 patent/US20060257673A1/en not_active Abandoned
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103824516A (zh) * | 2009-12-17 | 2014-05-28 | 3M创新有限公司 | 显示面板组件 |
CN103824516B (zh) * | 2009-12-17 | 2016-08-17 | 3M创新有限公司 | 显示面板组件 |
CN103665231A (zh) * | 2012-09-10 | 2014-03-26 | 中国石油化工集团公司 | 一种醋酸乙烯-乙烯-叔碳酸乙烯酯共聚乳液及合成方法 |
CN103665231B (zh) * | 2012-09-10 | 2016-09-14 | 中国石油化工集团公司 | 一种醋酸乙烯-乙烯-叔碳酸乙烯酯共聚乳液及合成方法 |
CN105026150A (zh) * | 2013-02-08 | 2015-11-04 | 株式会社可乐丽 | 多层结构体及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1721731A1 (de) | 2006-11-15 |
DE102005022166A1 (de) | 2006-11-16 |
US20060257673A1 (en) | 2006-11-16 |
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