EP1541751B1 - Use of protective colloid-stabilized polymers as double-point coatings - Google Patents
Use of protective colloid-stabilized polymers as double-point coatings Download PDFInfo
- Publication number
- EP1541751B1 EP1541751B1 EP03028481A EP03028481A EP1541751B1 EP 1541751 B1 EP1541751 B1 EP 1541751B1 EP 03028481 A EP03028481 A EP 03028481A EP 03028481 A EP03028481 A EP 03028481A EP 1541751 B1 EP1541751 B1 EP 1541751B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vinyl
- use according
- polymer
- acid
- protective colloid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 230000001681 protective effect Effects 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 239000000084 colloidal system Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- -1 alkyl carbonic acids Chemical class 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010022 rotary screen printing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 2
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 239000000693 micelle Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000004831 Hot glue Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 229960002900 methylcellulose Drugs 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ZHNUHDYFZUAESO-OUBTZVSYSA-N aminoformaldehyde Chemical compound N[13CH]=O ZHNUHDYFZUAESO-OUBTZVSYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- GOPSAMYJSPYXPL-UHFFFAOYSA-N prop-2-enyl n-(hydroxymethyl)carbamate Chemical compound OCNC(=O)OCC=C GOPSAMYJSPYXPL-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NVNRCMRKQVEOMZ-UHFFFAOYSA-N 1-ethoxypropane-1,2-diol Chemical compound CCOC(O)C(C)O NVNRCMRKQVEOMZ-UHFFFAOYSA-N 0.000 description 1
- DTEAMMSJXLXUOQ-UHFFFAOYSA-N 1-hydroxyaziridine Chemical compound ON1CC1 DTEAMMSJXLXUOQ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GWRKYBXTKSGXNJ-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxyperoxy)propane Chemical compound CC(C)COOOCC(C)C GWRKYBXTKSGXNJ-UHFFFAOYSA-N 0.000 description 1
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- OMSKWMHSUQZBRS-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid;sodium Chemical class [Na].OS(=O)(=O)C1=CC=C(C=C)C=C1 OMSKWMHSUQZBRS-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CZRCOWVNDIYQQC-UHFFFAOYSA-N COC(=O)C(O)NC(=O)C=CC Chemical compound COC(=O)C(O)NC(=O)C=CC CZRCOWVNDIYQQC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 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 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical class CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical class OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001456 poly(acrylic acid sodium salt) Polymers 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920006001 poly(vinyl alcohol-co-ethylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical class [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M17/00—Producing multi-layer textile fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M17/00—Producing multi-layer textile fabrics
- D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0092—Non-continuous polymer coating on the fibrous substrate, e.g. plastic dots on fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2205/00—Condition, form or state of the materials
- D06N2205/02—Dispersion
- D06N2205/023—Emulsion, aqueous dispersion, latex
Definitions
- the invention relates to the use of a protective colloid-stabilized polymer for coating a carrier material.
- such a material may be coated with a hot melt adhesive and then bonded to a second material placed thereon.
- a hot melt adhesive is coated with a hot melt adhesive and then bonded to a second material placed thereon.
- One possible coating is the so-called double dot coating.
- a sub-item is first printed on the material to be coated. This printing can be done by rotary screen printing.
- the sub-item is a paste comprising an aqueous dispersion of an emulsifier-stabilized polymer, thickener and, optionally, printing assistant.
- hot melt glue is scattered. Excess powder is sucked off. Thereafter, the sub-item is first dried and sintered with the hot melt adhesive, or the hot melt adhesive is melted.
- a coated sheet which comprises a coating carrier (also referred to herein as a carrier material), a base layer made thereon of a plastic compound (also referred to herein as a sub-point) and a second layer provided thereon (also referred to herein as a hot-melt adhesive) ,
- the basecoat is made from a crosslinkable, aqueous polymer dispersion, emulsion and / or solution.
- Self-crosslinking acrylic polymers, self-crosslinking polyvinyl esters or self-crosslinking styrene-acrylic or acrylic-vinyl ester copolymers have been used as polymer dispersions.
- the polymers used preferably have a film-forming temperature of at least 5 ° C. and are usually acidified in the dispersion or emulsion form.
- DE-A-3510109 describes the use of a protective colloid-stabilized polymer for the Punttberchichtung a carrier material.
- the present invention is therefore based on the object to overcome these disadvantages.
- this is achieved by the use of a protective colloid-stabilized polymer comprising a protective colloid and a polymer for the double-point coating of a carrier material.
- a protective colloid stabilized polymer can be used to coat a support material, e.g. textile material, suitable to stick it then, was completely surprising for the expert.
- Prerequisite for bonding textile materials is that the bond during washing or cleaning is not solved.
- protective colloid-stabilized polymers would expect protective colloid-stabilized polymers to be soluble, thus dissolving the adhesions made therefrom with fabrics during washing. Surprisingly, however, this was not observed. Rather, it has even been found that the bonds obtainable using protective colloid-stabilized polymers are very resistant to washing and cleaning.
- Emulsifiers are compounds which can be subsumed under the term "surfactants".
- Surfactants are compounds which can be subsumed under the term "surfactants".
- Protective colloids are surface-active substances, but they have very characteristic differences to surfactants.
- a characteristic feature of surfactants and their solutions is micelle formation. As the surfactant concentration increases, the number of molecules increases at the interface until there is no room for more. Then the time for the formation of micelles is given.
- the formation of micelles starts in a narrow range of concentration characteristic of each surfactant and depends on the molecular structure. It occurs at the concentration at which the surface is completely or substantially fully occupied and therefore the surface tension becomes independent of the increase in the concentration. By measuring the surface tension as a function of the concentration, the concentration at which the micelle formation begins can be determined in a simple manner. It is called the critical micelle concentration (CMC).
- CMC critical micelle concentration
- HLB value hydrophilic-lipophilic balance
- Protective colloid-stabilized polymers are known to the person skilled in the art. They are commercially available or can be prepared by free-radically initiated polymerization of monomers below and optionally auxiliary monomers.
- the free-radically initiated polymerization of the ethylenically unsaturated monomers can be carried out by suspension or emulsion polymerization. In suspension and emulsion polymerization, in the presence of surface-active substances of the composition, 100-51% of protective colloids and 0-49% of emulsifiers are polymerized.
- Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic radical and up to 60 ethylene or Propylene oxide units, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
- anionic surfactants such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the
- protective colloids are modified natural polymers, such as O-methylcellulose, O- (2-hydroxyethyl) -cellulose, O- (2-hydroxy-propyl) -cellulose, O- (2-hydroxy-propyl) -O-methyl-cellulose, O- (2-hydroxy-butyl) -O-methyl-cellulose, carboxymethylcellulose (Na salt), starch ether, O- (2-hydroxy-propyl) starch and lignosulfonic acid, synthetic homo- and Copolymers such as poly (vinyl alcohol) [partially hydrolyzed poly (vinyl acetate)], poly (vinyl alcohol-co-ethylene), poly (methacrylic acid-sodium salts), poly [methacrylic acid-sodium-salt-co- (methacrylic acid-methyl ester)] ], Poly [acrylic acid-co-acrylic acid (2-ethyl-hexyl ester)], poly [methacrylic acid (hydroxyl-alkyl ester)],
- the polymers of the protective colloid-stabilized polymer are explained in more detail below with reference to the monomers.
- polymers are to be understood as meaning both homopolymers and copolymers.
- the monomers may be ethylenically unsaturated monomers.
- vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms acrylic esters or methacrylic esters of branched or unbranched alcohols or diols having 1 to 18 carbon atoms, C 2 -C 20 -mono- or di-carboxylic acids, their amides , N-methylolamides or nitriles, C2-C20-sulphonic acids, 3-20-membered heterocyclic compounds with oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, boron or aluminum as heteroatom, dienes with at least 4 C atoms, olefins with at least 2 C atoms, vinyl aromatics in particular with benzene or naphthalene as aromatic, and C2-C20 vinyl halides.
- Preferred vinyl esters are those having 1 to 12 C atoms, in particular vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 13 C atoms.
- the acrylic acid or methacrylic ester is an ester of unbranched or branched alcohols having 1 to 15 C atoms, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate and 2-ethylhexyl acrylate, more particularly methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate.
- Preferred mono- and di-carboxylic acids, their amides, N-methylol amides and nitriles are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide, N-methylolacrylamide, N-methylolmethacrylamide and acrylonitrile.
- the sulfonic acid is desirably selected from vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid.
- the preferred heterocyclic compounds are vinylpyrrolidone and vinylpyridine.
- the vinyl aromatic is styrene, methyl styrene or vinyl toluene.
- the vinyl halide is vinyl chloride.
- the olefin is selected from ethylene and propylene.
- Preferred dienes are selected from 1,3-butadiene and isoprene.
- a plurality of different protective colloid-stabilized polymers can be used.
- auxiliary monomers are copolymerized.
- auxiliary monomers are ethylenically unsaturated C 2 -C 20 -mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated C 2 -C 20 -carboxylic acid amides and nitrites, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid, such as diethyl and diisopropyl esters, and maleic anhydride, ethylenically unsaturated C 2 -C 20 -sulfonic acids or their salts (alkali, alkaline earth and ammonium salts), preferably vinylsulfonic acid, 2-acryl
- C2-C20 comonomers such as polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, diallyl phthalate, allyl methacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylolyglycolic acid (AGA), methylacrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N Methylolmethacrylamide, N-methylolallylcarbamate, C 2 -C 20 -alkyl ethers such as the isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate.
- AGA acrylolyglycolic acid
- MAGME methylacrylamidoglycolic acid methyl ester
- NMA N-methylolacrylamide
- NMA N Methylolme
- epoxide-functional C 2 -C 20 comonomers such as glycidyl methacrylate and glycidyl acrylate.
- silicon-functional C 2 -C 20 comonomers such as acryloxypropyltri (alkoxy) - and methacryloxypropyltri (alkoxy) silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where as alkoxy groups, for example, ethoxy and ethoxypropylene glycol ether radicals may be present.
- C 2 -C 20 -monomers having hydroxyl or CO groups for example methacrylic acid and acrylic acid hydroxyalkyl esters, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.
- the properties of the coatings can be favorably influenced.
- the polymers are particularly preferably prepared from monomers or mixtures which contain one or more monomers from the group of vinyl acetate, vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 13 C atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate , n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate or styrene.
- mixtures of vinyl acetate with ethylene of vinyl acetate, ethylene and a vinyl ester of ⁇ -branched monocarboxylic acids having 9 to 13 carbon atoms; of n-butyl acrylate, 2-ethylhexyl acrylate and / or methyl methacrylate; of styrene with one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; of vinyl acetate with one or more monomers from the group of methyl acrylate.
- These blends have been found to be particularly beneficial because they exhibit excellent coating properties at low cost.
- the monomer selection or the selection of the weight proportions of the comonomers can be carried out so that in general a glass transition temperature Tg of -50 ° C to + 120 ° C, preferably -30 ° C to + 95 ° C results.
- the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC).
- Tgn the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd edition, J. Wiley & Sons, New York (1975).
- the polymerization of the above monomers and optionally auxiliary monomers to the polymer can be radicalized.
- the free-radically initiated polymerization of the ethylenically unsaturated monomers can be carried out by suspension polymerization and emulsion polymerization.
- the polymerization temperature may be 40 ° C to 100 ° C, preferably 60 ° C to 90 ° C.
- gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride
- initiation of the polymerization can be carried out with the customary water-soluble or monomer-soluble initiators or redox initiator combinations take place. Examples of water-soluble initiators are the sodium.
- monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate.
- the initiators mentioned are generally in an amount of 0.01 to 10.0 wt .-%. preferably 0.1 to 0.5 wt.%, in each case based on the total weight of the monomers, used as redox initiators, combinations of said initiators with reducing agents can be used.
- Suitable reducing agents are the sulfites and bisulfites of the alkali metals and of ammonium, for example sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or Alkaliformaldehydsulfoxylate, for example Natriumhydroxymethansulfinat, and ascorbic acid.
- the amount of reducing agent is generally from 0.01 to 10.0 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the total weight of the monomers.
- the monomers can be submitted in total, be metered in total or be introduced in portions and the remainder be added after the initiation of the polymerization.
- the dosages can be carried out separately (spatially and temporally) or the components to be metered can be added all or partly pre-emulsified.
- the present invention has a number of advantages. First of all, it has been found that, in comparison to other prior art coating processes, very small amounts of coating suffice for sufficiently good adhesion. As a result, a significant reduction in costs can be achieved, and the bonded textile materials have a pleasant soft touch. With the protective colloid-stabilized polymers used according to the invention, a very high adhesive strength of the bonded textiles is observed. The connection of the scattering powder to the sub-point is very good. The bonds obtained with the coating using a protective colloid-stabilized polymer are very good for washing and cleaning.
- the sub-point obtained with the protective colloid-stabilized polymer does not penetrate into the textile substrate during the double-point coating, ie a very effective flashback is achieved. Furthermore, pastes containing the protective colloid-stabilized polymer and to Making the subpoint used in colon coatings, has a very good rheology and does not dry on the template.
- the protective colloid-stabilized polymers can be used in the form of a paste.
- a dispersion of the protective colloid-stabilized polymer in water is used.
- the amount of water may be, for example, 70% by weight, based on the dispersion, and that of the protective-colloid-stabilized polymer 30% by weight, likewise based on the dispersion.
- Thickeners and, if appropriate, printing assistants can then be added to these polymer dispersions, as a result of which pastes for coating are obtained.
- These pastes can be applied, for example, in rotary screen printing on the substrate to be coated. In this way, a sub-point for the double-point coating can be produced. On the sub-point can then be sprinkled hot melt adhesive powder. Excess powder can subsequently be removed by suction. The sub-item can then be dried and sintered, or the litter powder can be melted.
- the abovementioned polymer dispersions have the advantage that they are obtained by adding compounds having 2 or more epoxide, organo, halogen, hydroxyl, aziridine, carbodiimide, oxazoline, alcohol, amine, aminosilane, aminoformaldehyde, Isocyanate or N-2-hydroxyalkylamide residues can be crosslinked.
- crosslinking of the polymer with the protective colloid shell and with the added additives also occurs. As a result, particularly high adhesive strengths are achieved.
- Crosslinkers may also be present in the final formulation of the dispersion or paste, for example compounds containing two or more epoxy, organo, halogen, hydroxy, aziridine, carbodiimide, oxazoline, alcohol, amine, aminosilane, Amino-formaldehyde, isocyanate or N-2-hydroxyalkylamide residues.
- the substrates that can be coated can be materials of any kind. It can be flexible, not very flexible or not flexible at all. Examples are textile materials of any kind, such as woven, knitted, woven knitted fabric, Raschelwaren (natural and synthetic fibers). Flies made of any material. Furthermore, films can be coated, in particular of plastics of any kind, as well as paper, synthetic leather, leather, foam and wood.
- Tebelink® B-IC polysocyanate, modified, Dr. med. Th. Boehme KG Chem. Fabrik GmbH & Co.
- Tebelink® MFA partially etherified, modified melamine-formaldehyde condensate, low in formaldehyde (0.3%), Dr. Ing. Th. Boehme KG Chem. Fabrik GmbH & Co.
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- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
Die Erfindung betrifft die Verwendung eines schutzkolloidstabilisierten Polymers zur Beschichtung eines Trägermaterials.The invention relates to the use of a protective colloid-stabilized polymer for coating a carrier material.
Zur Verklebung von textilen Materialien kann beispielsweise ein solches Material mit einem Schmelzklebepulver beschichtet und dann mit einem zweiten, darauf gelegten Material verklebt werden. Eine mögliche Beschichtung ist die sogenannte Doppelpunktbeschichtung (double dot coating). Dabei wird auf das zu beschichtende Material zunächst ein Unterpunkt aufgedruckt. Dieses Bedrucken kann durch Rotationssiebdruck erfolgen. Bei dem Unterpunkt handelt es sich um eine Paste, die eine wäßrige Dipersion eines emulgatorstabilisierten Polymers, Verdicker und gegebenenfalls Druckhilfsmittel umfaßt. Auf den noch nassen Unterpunkt wird dann Schmelzklebepulver aufgestreut. Überschüssiges Pulver wird abgesaugt. Danach wird der Unterpunkt mit dem Schmelzklebepulver zunächst getrocknet und angesintert, oder das Schmelzklebepulver wird aufgeschmolzen.For bonding textile materials, for example, such a material may be coated with a hot melt adhesive and then bonded to a second material placed thereon. One possible coating is the so-called double dot coating. In this case, a sub-item is first printed on the material to be coated. This printing can be done by rotary screen printing. The sub-item is a paste comprising an aqueous dispersion of an emulsifier-stabilized polymer, thickener and, optionally, printing assistant. On the still wet sub-point then hot melt glue is scattered. Excess powder is sucked off. Thereafter, the sub-item is first dried and sintered with the hot melt adhesive, or the hot melt adhesive is melted.
Ein Beispiel einer Doppelpunktbeschichtung wird in der EP 0 547 261 B1 beschrieben. Dort wird ein beschichtetes Flächengebilde offenbart, das einen Beschichtungsträger (vorliegend auch als Trägermaterial bezeichnet), eine darauf aufgebrachte Grund- bzw. Basisschicht aus einer Kunststoffmasse (vorliegend auch als Unterpunkt bezeichnet) und eine darauf vorgesehene zweite Schicht (vorliegend auch als Schmelzkleber bezeichnet) umfaßt. Die Grundschicht ist aus einer vernetzbaren, wäßrigen Polymerdispersion, -emulsion und/oder - lösung hergestellt. Als Polymerdispersionen wurden selbstvemetzende Acrylpolymere, selbstvemetzende Polyvinylester oder selbstvemetzende Styrol-Acryl- oder Acryl-Vinylester-Copolymere verwendet. Die verwendeten Polymere haben vorzugsweise eine Filmbildungstemperatur von mindestens 5°C und sind in Dispersions- oder Emulsionsform meist sauer eingestellt.An example of a double-point coating is described in EP 0 547 261 B1. There, a coated sheet is disclosed which comprises a coating carrier (also referred to herein as a carrier material), a base layer made thereon of a plastic compound (also referred to herein as a sub-point) and a second layer provided thereon (also referred to herein as a hot-melt adhesive) , The basecoat is made from a crosslinkable, aqueous polymer dispersion, emulsion and / or solution. Self-crosslinking acrylic polymers, self-crosslinking polyvinyl esters or self-crosslinking styrene-acrylic or acrylic-vinyl ester copolymers have been used as polymer dispersions. The polymers used preferably have a film-forming temperature of at least 5 ° C. and are usually acidified in the dispersion or emulsion form.
Nachteilig an dieser Doppelpunktbeschichtung sind die Haftwerte für die Verklebungen nach Wäsche und chemischer Reinigung. Das rheologische Verhalten und das Antrocknen der Paste auf der Schablone beim Rotationssiebdruck ergeben ein schlechtes Verarbeitungsverhalten.Disadvantages of this double-point coating are the adhesion values for the adhesions after washing and chemical cleaning. The rheological behavior and the drying of the paste on the stencil during rotary screen printing result in a poor processing behavior.
DE-A-3510109 beschreibt die Verwendung eines schutzkolloidstabilisierten Polymers zur Punttberchichtung eines Trägermaterials.DE-A-3510109 describes the use of a protective colloid-stabilized polymer for the Punttberchichtung a carrier material.
Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, diese Nachteile auszuräumen.The present invention is therefore based on the object to overcome these disadvantages.
Erfindungsgemäß wird dies durch die Verwendung eines schutzkolloidstabilisierten Polymers, umfassend ein Schutzkolloid und ein Polymer, zur Doppelpunktbeschichtung eines Trägermaterials gelöst.According to the invention, this is achieved by the use of a protective colloid-stabilized polymer comprising a protective colloid and a polymer for the double-point coating of a carrier material.
Daß sich ein schutzkolloidstabilisiertes Polymer überhaupt zur Beschichtung eines Trägermaterials, z.B. textilen Materials, eignet, um es dann zu verkleben, war für den Fachmann vollkommen überraschend. Voraussetzung zum Verkleben von textilen Materialien ist, daß die Verklebung beim Waschen bzw. beim Reinigen nicht gelöst wird. Der Fachmann erwartet aber, daß schutzkolloidstabilisierte Polymere löslich sind und somit die daraus hergestellten Verklebungen mit Textilien beim Waschen aufgelöst werden. Überraschenderweise wurde dies aber nicht beobachtet. Es wurde vielmehr sogar gefunden, daß die unter Verwendung von schutzkolloidstabilisierten Polymeren erhältlichen Verklebungen sehr wasch- und reinigungsbeständig sind.That a protective colloid stabilized polymer can be used to coat a support material, e.g. textile material, suitable to stick it then, was completely surprising for the expert. Prerequisite for bonding textile materials is that the bond during washing or cleaning is not solved. However, those skilled in the art would expect protective colloid-stabilized polymers to be soluble, thus dissolving the adhesions made therefrom with fabrics during washing. Surprisingly, however, this was not observed. Rather, it has even been found that the bonds obtainable using protective colloid-stabilized polymers are very resistant to washing and cleaning.
Bei den bisher nach dem Stand der Technik für Beschichtungen, insbesondere Doppelpunktbeschichtungen, eingesetzten Polymeren handelt es sich u.a. um emulgatorstabilisierte Polymere. Emulgatoren sind Verbindungen, die unter dem Begriff "Tenside" subsummiert werden können. Auch Schutzkolloide sind grenzflächenaktive Substanzen, allerdings weisen sie ganz charakteristische Unterschiede zu Tensiden auf. Eine charakteristische Eigenschaft von Tensiden und ihren Lösungen ist die Mizellenbildung. Mit zunehmender Tensidkonzentration steigt an der Grenzfläche die Zahl der Moleküle so lange, bis es keinen Platz für weitere gibt. Dann ist der Zeitpunkt für die Bildung von Mizellen gegeben. Man bezeichnet abgelöste Aggregate einer größeren Anzahl von Tensidmolekülen oder Ionen als Mizellen. Sie sind dynamische Gebilde, die mit der sie umgebenden Lösung im Gleichgewicht stehen. Die Bildung von Mizellen setzt in einem eng begrenzten, für jedes Tensid charakteristischen Konzentrationsbereich ein und ist vom Molekülaufbau abhängig. Sie tritt bei der Konzentration ein, bei der die Oberfläche vollständig bzw. weitgehend vollständig belegt ist und daher die Oberflächenspannung unabhängig von der Erhöhung der Konzentration wird. Durch die Messung der Oberflächenspannung in Abhängigkeit von der Konzentration läßt sich in einfacher Weise die Konzentration ermitteln, bei der die Mizellenbildung beginnt. Sie wird die kritische Mizellbildungskonzentration (CMC) genannt. Des weiteren wurde zur Charakterisierung von Tensiden der Begriff "HLB-Wert" (hydrophilic-lipophilic balance) eingeführt. Dabei werden die Tenside nach den hydrophilen und hydrophoben Gruppen unter Berücksichtigung der Struktur charakterisiert. Die Bestimmung des HLB-Wertes beruht auf empirischer Basis: 
wobei M0 das Gewicht des hydrophoben Molekülteils und M das gesamte Molekulargewicht bezeichnet.The polymers used to date for coatings, in particular double-dot coatings, are, inter alia, emulsifier-stabilized polymers. Emulsifiers are compounds which can be subsumed under the term "surfactants". Protective colloids are surface-active substances, but they have very characteristic differences to surfactants. A characteristic feature of surfactants and their solutions is micelle formation. As the surfactant concentration increases, the number of molecules increases at the interface until there is no room for more. Then the time for the formation of micelles is given. One refers to detached aggregates of a larger number of surfactant molecules or ions as micelles. They are dynamic entities in equilibrium with the surrounding solution. The formation of micelles starts in a narrow range of concentration characteristic of each surfactant and depends on the molecular structure. It occurs at the concentration at which the surface is completely or substantially fully occupied and therefore the surface tension becomes independent of the increase in the concentration. By measuring the surface tension as a function of the concentration, the concentration at which the micelle formation begins can be determined in a simple manner. It is called the critical micelle concentration (CMC). Furthermore, the term "HLB value" (hydrophilic-lipophilic balance) was introduced for the characterization of surfactants. The surfactants under the hydrophilic and hydrophobic groups under Considering the structure is characterized. The determination of the HLB value is based on empirical data:
where M0 denotes the weight of the hydrophobic moiety and M denotes the total molecular weight.
Sowohl die kritische Mizellbildungskonzentration als auch der HLB-Wert sind charakteristische Eigenschaften von Tensiden und ihren Lösungen. Beide Eigenschaften haben die Schutzkolloide nicht.Both the critical micelle formation concentration and the HLB value are characteristic properties of surfactants and their solutions. Both properties do not have the protective colloids.
Schutzkolloidstabilisierte Polymere sind dem Fachmann bekannt. Sie sind kommerziell erhältlich oder können durch radikalisch initiierte Polymerisation untenstehender Monomere und ggf. Hilfsmonomere hergestellt werden. Die radikalisch initiierte Polymerisation der ethylenisch ungesättigten Monomeren kann durch Suspensions- oder Emulsionspolymerisation erfolgen. Bei der Suspensions- und Emulsionspolymerisation wird in Gegenwart von oberflächenaktiven Substanzen der Zusammensetzung von 100-51 % Schutzkolloiden und 0-49 % Emulgatoren polymerisiert. Geeignete Emulgatoren sind sowohl anionische, kationische als auch nichtionische Emulgatoren, beispielsweise anionische Tenside, wie Alkylsulfate mit einer Kettenlänge von 8 bis 18 C-Atomen, Alkyl- oder Alkylarylethersulfate mit 8 bis 18 C-Atomen im hydrophoben Rest und bis zu 60 Ethylen- oder Propylenoxideinheiten, Alkyl- oder Alkylarylsulfonate mit 8 bis 18 C-Atomen, Ester und Halbester der Sulfobemsteinsäure mit einwertigen Alkoholen oder Alkylphenolen, oder nichtionische Tenside wie Alkytpolyglykolether oder Alkylarylpolyglykolether mit bis zu 60 Ethylenoxid- bzw. Propylenoxid-Einheiten.Protective colloid-stabilized polymers are known to the person skilled in the art. They are commercially available or can be prepared by free-radically initiated polymerization of monomers below and optionally auxiliary monomers. The free-radically initiated polymerization of the ethylenically unsaturated monomers can be carried out by suspension or emulsion polymerization. In suspension and emulsion polymerization, in the presence of surface-active substances of the composition, 100-51% of protective colloids and 0-49% of emulsifiers are polymerized. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic radical and up to 60 ethylene or Propylene oxide units, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
Besonderes bevorzugte Vertreter für Schutzkolloide sind modifizierte natürliche Polymere, wie O-Methyl-cellulose, O-(2-Hydroxy-ethyl)-cellulose, O-(2-Hydroxy-propyl)-cellulose, O-(2-Hydroxy-propyl)-O-methyl-cellulose, O-(2-Hydroxy-butyl)-O-methyl-cellulose, Carboxymethylcellulose (Na-Salz), Stärkeether, O-(2-Hydroxy-propyl)-stärke und Ligninsulfonsäure, synthetische Homo- und Copolymerisate, wie Poly(vinylalkohol) [teilverseiftes Poly(vinylacetat)], Poly(vinylalkohol-co-ethylen), Poly(methacrylsäure-Natrium-Salze), Poly[methacrylsäure-Natrium-Salz-co-(methacryl-säure-methylester)], Poly[acrylsäure-co-acrylsäure-(2-ethyl-hexylester)], Poly[methacrylsäure-(hydroxyl-alkylester)], Poly(styrol-co-maleinsäure-Natrium-Salz), Poly(styrol-4-sulfonsäure-Natrium-Salz-co-maleinsäure-halbester), Poly(ethylene-co-maleinsäure-partial-ester)Poly(oxiran), Poly(alkyl)-vinyl-ether), Poly(acrylsäure-Natrium-Salz), Poly-(alkyl-vinylether-co-maleinsäure-anhydrid), Poly(vinylacetat-co-maleinsäure-anhydrid), Poly(1-vinyl-2-pyrrolidon), Poly[(1-vinyl-2-pyrrolidon)-co-methacryl-säure-alkylester], Poly[(1-vinyl-2-pyrrolidon)-co-methacrylamid], Poly(vinyl-pyridin) und Poly(dially-dimethyl-ammoniumchlorid), Ptropf-Polymerisate, wie Poly(vinylchlorid-g-vinylalkohol), Poly(styrol-g-vinylalkohol), Poly-(styrol-g-acrylsäure), Poly(styrol-g-(1-vinyl-2-pyrrolidon)] und Poly[acrylsäure-tert.-butylester-g-(1-vinyl-2-pyrrolidon)], sowie Kondensationsprodukte, wie Harnstoff-Formaldehyd-Kondensate, Phenol-Formaldehyd-Kondensate und Alkydharze.Particularly preferred representatives of protective colloids are modified natural polymers, such as O-methylcellulose, O- (2-hydroxyethyl) -cellulose, O- (2-hydroxy-propyl) -cellulose, O- (2-hydroxy-propyl) -O-methyl-cellulose, O- (2-hydroxy-butyl) -O-methyl-cellulose, carboxymethylcellulose (Na salt), starch ether, O- (2-hydroxy-propyl) starch and lignosulfonic acid, synthetic homo- and Copolymers such as poly (vinyl alcohol) [partially hydrolyzed poly (vinyl acetate)], poly (vinyl alcohol-co-ethylene), poly (methacrylic acid-sodium salts), poly [methacrylic acid-sodium-salt-co- (methacrylic acid-methyl ester)] ], Poly [acrylic acid-co-acrylic acid (2-ethyl-hexyl ester)], poly [methacrylic acid (hydroxyl-alkyl ester)], poly (styrene-co-maleic acid-sodium salt), poly (styrene-4-sulfonic acid Sodium salt-co-maleic acid half ester), poly (ethylene-co-maleic acid-partial-ester) poly (oxirane), poly (alkyl) -vinyl-ether), poly (acrylic acid-sodium salt), poly (ethylene oxide) (alkyl vinyl ether-co-maleic anhydride), poly (vinyl acetate-co-malein acid anhydride), poly (1-vinyl-2-pyrrolidone), poly [(1-vinyl-2-pyrrolidone) -co-methacrylic acid alkyl ester], poly [(1-vinyl-2-pyrrolidone) -co methacrylamide] Poly (vinyl pyridine) and poly (diallyl dimethyl ammonium chloride), graft polymers such as poly (vinyl chloride-g-vinyl alcohol), poly (styrene-g-vinyl alcohol), poly (styrene-g-acrylic acid), poly (styrene-g- (1-vinyl-2-pyrrolidone)] and poly [acrylic acid tert-butyl ester g- (1-vinyl-2-pyrrolidone)], as well as condensation products such as urea-formaldehyde condensates, phenol Formaldehyde condensates and alkyd resins.
Die Polymere des schutzkolloidstabilisierten Polymers werden nachfolgend anhand der Monomeren näher erläutert. Unter Polymeren im Sinn der vorliegenden Erfindung sind sowohl Homo- als auch Copolymere zu verstehen. Bei den Monomeren kann es sich um ethylenisch ungesättigte Monomere handeln. Diese können ausgewählt sein unter Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 18 C-Atomen, Acrylsäureester oder Methacrylsäureester von verzweigten oder unverzweigten Alkoholen oder Diolen mit 1 bis 18 C-Atomen, C2-C20-Mono- oder Di-Carbonsäuren, deren Amide, N-Methylolamide oder Nitrile, C2-C20-Sulfonsäuren, 3-20-gliedrige heterocyclische Verbindungen mit Sauerstoff, Schwefel, Selen, Tellur, Stickstoff, Phosphor, Bor oder Aluminium als Heteroatom, Diene mit mindestens 4 C-Atomen, Olefine mit mindestens 2 C-Atomen, Vinylaromaten insbesondere mit Benzol oder Naphthalein als Aromat, und C2-C20 Vinylhalogeniden.The polymers of the protective colloid-stabilized polymer are explained in more detail below with reference to the monomers. For the purposes of the present invention, polymers are to be understood as meaning both homopolymers and copolymers. The monomers may be ethylenically unsaturated monomers. These may be selected from vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms, acrylic esters or methacrylic esters of branched or unbranched alcohols or diols having 1 to 18 carbon atoms, C 2 -C 20 -mono- or di-carboxylic acids, their amides , N-methylolamides or nitriles, C2-C20-sulphonic acids, 3-20-membered heterocyclic compounds with oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, boron or aluminum as heteroatom, dienes with at least 4 C atoms, olefins with at least 2 C atoms, vinyl aromatics in particular with benzene or naphthalene as aromatic, and C2-C20 vinyl halides.
Bevorzugte Vinylester sind solche mit 1 bis 12-C-Atomen, insbesondere Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Vinyllaurat, 1-Methylvinylacetat, Vinylpivalat und Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen.Preferred vinyl esters are those having 1 to 12 C atoms, in particular vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 13 C atoms.
In einer weiteren bevorzugten Ausführungsform ist der Acrylsäure oder Methacrylsäureester ein Ester von unverzweigten oder verzweigten Alkoholen mit 1 bis 15 C-Atomen, insbesondere Methytacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, t-Butylacrylat, t-Butylmethacrylat und 2-Ethylhexylacrylat, ganz besonders Methylacrylat, Methylmethadrylat, n-Butylacrylat, t-Butylacrylat, und 2-Ethythexylacrylat.In a further preferred embodiment, the acrylic acid or methacrylic ester is an ester of unbranched or branched alcohols having 1 to 15 C atoms, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate and 2-ethylhexyl acrylate, more particularly methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate.
Bevorzugte Mono- und Di-Carbonsäuren, deren Amide, N-Methylolamide und Nitrile sind ausgewählt unter Acrlssäure, Methacrylsäure, Fumarsäure, Maleinsäure, Acrylamid, N-Methylolacrylamid, N-Methylolmethacrylamid und Acrylnitril.Preferred mono- and di-carboxylic acids, their amides, N-methylol amides and nitriles are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide, N-methylolacrylamide, N-methylolmethacrylamide and acrylonitrile.
Die Sulfonsäure ist günstigerweise unter Vinylsulfonsäure und 2-Acrylamido-2-methylpropansulfonsäure ausgewählt. Die bevorzugten heterocyclischen Verbindungen sind Vinylpyrrolidon und Vinylpyridin.The sulfonic acid is desirably selected from vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. The preferred heterocyclic compounds are vinylpyrrolidone and vinylpyridine.
Vorzugsweise ist der Vinylaromat Styrol, Methylstyrol oder Vinyltoluol.Preferably, the vinyl aromatic is styrene, methyl styrene or vinyl toluene.
Vorzugsweise ist das Vinylhalogenid Vinylchlorid.Preferably, the vinyl halide is vinyl chloride.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung wird das Olefin ausgewählt unter Ethylen und Propylen.In a preferred embodiment of the use according to the invention, the olefin is selected from ethylene and propylene.
Bevorzugte Diene werden unter 1,3-Butadien und Isopren ausgewählt.Preferred dienes are selected from 1,3-butadiene and isoprene.
Bei der erfindungsgemäßen Verwendung können mehrere, voneinander verschiedene schutzkolloidstabilisierte Polymere eingesetzt werden.In the use according to the invention, a plurality of different protective colloid-stabilized polymers can be used.
Gegebenenfalls können noch 0,1 bis 50 Gew.-%, bezogen auf das Gesamtgewicht des Monomergemisches, Hilfsmonomere copolymerisiert werden. Bevorzugt werden 0,5 bis 15 Gew.-% Hilfsmonomere eingesetzt. Beispiele für Hilfsmonomere sind ethylenisch ungesättigte C2-C20-Mono- und Dicarbonsäuren, vorzugsweise Acrylsäure, Methacrylsäure, Fumarsäure und Maleinsäure; ethylenisch ungesättigte C2-C20-Carbonsäureamide und -nitrile, vorzugsweise Acrylamid und Acrylnitril; Mono- und Diester der Fumarsäure und Maleinsäure wie die Diethyl- und Diisopropylester, sowie Maleinsäureanhydrid, ethylenisch ungesättigte C2-C20-Sulfonsäuren bzw. deren Salze (Alkali, Erdalkali und Ammonium-Salze), vorzugsweise Vinylsulfonsäure, 2-Acrylamido-2-methyl-propansulfonsäure. Weitere Beispiele sind vorvemetzende C2-C20-Comonomere, wie mehrfach ethylenisch ungesättigte Comonomere, beispielsweise Divinyladipat, Diallylmaleat, Diallylphthalat, Allylmethacrylat oder Triallylcyanurat, oder nachvemetzende Comonomere, beispielsweise Acrlyamidoglykolsäure (AGA), Methylacrylamidoglykolsäuremethylester (MAGME), N-Methylolacrylamid (NMA), N-Methylolmethacrylamid, N-Methylolallylcarbamat, C2-C20-Alkylether, wie der Isobutoxyether oder Ester des N-Mehtylolacrylamids, des N-Methylolmethacrlyamids und des N-Methylolallylcarbamats. Geeignet sind auch epoxidfunktionelle C2-C20-Comonomere wie Glycidylmethacrylat und Glycidylacrylat. Weitere Beispiele sind siliciumfunktionelle C2-C20-Comonomere wie Acryloxypropyltri(alkoxy)- und Methacryloxypropyltri(alkoxy)-Silane, Vinyltrialkoxysilane und Vinylmethyldialkoxysilane, wobei als Alkoxygruppen beispielsweise Ethoxy- und Ethoxypropylenglykolether-Reste enthalten sein können. Genannt seien auch C2-C20-Monomere mit Hydroxy- oder CO-Gruppen, beispielsweise Methacrylsäure- und Acrylsäurehydroxyalkylester, wie Hydroxyethyl-, Hydroxypropyl- oder Hydroxybutylacrylat oder -methacrylat sowie Verbindungen wie Diacetonacrylamid und Acetylacetoxyethylacrylat oder -methacrylat.Optionally, from 0.1 to 50 wt .-%, based on the total weight of the monomer mixture, auxiliary monomers are copolymerized. Preferably, 0.5 to 15 wt .-% auxiliary monomers are used. Examples of auxiliary monomers are ethylenically unsaturated C 2 -C 20 -mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated C 2 -C 20 -carboxylic acid amides and nitrites, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid, such as diethyl and diisopropyl esters, and maleic anhydride, ethylenically unsaturated C 2 -C 20 -sulfonic acids or their salts (alkali, alkaline earth and ammonium salts), preferably vinylsulfonic acid, 2-acrylamido-2-methyl- propane sulfonic acid. Further examples are predominantly C2-C20 comonomers, such as polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, diallyl phthalate, allyl methacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylolyglycolic acid (AGA), methylacrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N Methylolmethacrylamide, N-methylolallylcarbamate, C 2 -C 20 -alkyl ethers such as the isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate. Also suitable are epoxide-functional C 2 -C 20 comonomers, such as glycidyl methacrylate and glycidyl acrylate. Further examples are silicon-functional C 2 -C 20 comonomers, such as acryloxypropyltri (alkoxy) - and methacryloxypropyltri (alkoxy) silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where as alkoxy groups, for example, ethoxy and ethoxypropylene glycol ether radicals may be present. Also mentioned are C 2 -C 20 -monomers having hydroxyl or CO groups, for example methacrylic acid and acrylic acid hydroxyalkyl esters, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.
Durch die Copolymerisation der vorstehend beschriebenen Monomeren mit den Hilfsmonomeren können die Eigenschaften der Beschichtungen, wie Haftung, Vernetzung und Stabilisierung, in günstiger Weise beeinflußt werden.By copolymerizing the monomers described above with the auxiliary monomers, the properties of the coatings, such as adhesion, crosslinking and stabilization, can be favorably influenced.
Besonders bevorzugt werden die Polymere aus Monomeren oder Gemischen hergestellt, welche ein oder mehrere Monomere aus der Gruppe Vinylacetat, Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen, Vinylchlorid, Ethylen, Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, 2-Ethylhexylacrylat oder Styrol enthalten. Am meisten bevorzugt werden Gemische von Vinylacetat mit Ethylen; von Vinylacetat, Ethylen und einem Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen; von n-Butylacrylat, 2-Ethylhexylacrylat und/oder Methylmethacrylat; von Styrol mit einem oder mehreren Monomeren aus der Gruppe Methylacrylat, Ethylacrylat, Propylacrylat n-Butylacrylat, 2-Ethylhexylacrylat; von Vinylacetat mit einem oder mehreren Monomeren aus der Gruppe Methylacrylat. Ethylacrylat, Propylacrylat, n-Butytacrylat, 2-Ethylhexylacrylat und gegebenenfalls Ethylen; wobei die genannten Gemisch gegebenenfalls noch ein oder mehrere der obengenannten Hilfsmonomere enthalten können. Diese Gemische haben sich als besonders günstig erwiesen, da sie bei niedrigen Kosten hervorragende Eigenschaften in Beschichtungen zeigen.The polymers are particularly preferably prepared from monomers or mixtures which contain one or more monomers from the group of vinyl acetate, vinyl esters of α-branched monocarboxylic acids having 9 to 13 C atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate , n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate or styrene. Most preferred are mixtures of vinyl acetate with ethylene; of vinyl acetate, ethylene and a vinyl ester of α-branched monocarboxylic acids having 9 to 13 carbon atoms; of n-butyl acrylate, 2-ethylhexyl acrylate and / or methyl methacrylate; of styrene with one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; of vinyl acetate with one or more monomers from the group of methyl acrylate. Ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; wherein said mixtures may optionally contain one or more of the above auxiliary monomers. These blends have been found to be particularly beneficial because they exhibit excellent coating properties at low cost.
Die Monomerauswahl bzw. die Auswahl der Gewichtsanteile der Comonomere kann so erfolgen, daß im allgemeinen eine Glasübergangstemperatur Tg von -50°C bis +120°C, vorzugsweise -30°C bis +95°C resultiert. Die Glasübergangstemperatur Tg der Polymerise kann in bekannter Weise mittels Differential Scanning Calorimetry (DSC) ermittelt werden. Die Tg kann auch mittels der Fox-Gleichung näherungsweise vorausberechnet werden. Nach Fox T. G., Bull. Am. Physics Soc. 1, 3, S. 123 (1956) gilt: 1/Tg = x1/Tg1 + x2/Tg2 + ... + xn/Tgn, wobei xn für den Massebruch (Gew.-%/100) des Monomeren n steht, und Tgn die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n ist. Tg-Werte für Homopolymerisate sind in Polymer Handbook 2nd Auflage, J. Wiley & Sons, New York (1975) aufgeführt.The monomer selection or the selection of the weight proportions of the comonomers can be carried out so that in general a glass transition temperature Tg of -50 ° C to + 120 ° C, preferably -30 ° C to + 95 ° C results. The glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be approximated by the Fox equation. After Fox T.G., Bull. Am. Physics Soc. 1, 3, p. 123 (1956): 1 / Tg = x1 / Tg1 + x2 / Tg2 + ... + xn / Tgn, where xn represents the mass fraction (wt .-% / 100) of the monomer n, and Tgn is the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd edition, J. Wiley & Sons, New York (1975).
Die Polymerisation vorstehender Monomere und ggf. Hilfsmonomere zum Polymer kann radikalisch intiiert werden. Die radikalisch initiierte Polymerisation der ethylenisch ungesättigten Monomeren kann durch Suspensionspolymerisation und Emulsionspolymerisation erfolgen.The polymerization of the above monomers and optionally auxiliary monomers to the polymer can be radicalized. The free-radically initiated polymerization of the ethylenically unsaturated monomers can be carried out by suspension polymerization and emulsion polymerization.
Die Polymerisationstemperatur kann 40°C bis 100°C, vorzugsweise 60°C bis 90°C, betragen. Bei der Copolymerisation von gasförmigen Comonomeren, wie Ethylen, 1,3-Butadien oder Vinylchlorid, kann auch unter Druck, im allgemeinen zwischen 5 bar und 100 bar, gearbeitet werden. Die Initiierung der Polymerisation kann mit den gebräuchlichen wasserlöslichen bzw. monomerlöslichen Initiatoren oder Redox-Initiator-Kombinationen erfolgen. Beispiele für wasserlösliche Initiatoren sind die Natrium-. Kalium- und Ammoniumsalze der Peroxodischwefelsäure, Wasserstoffperoxid, t-Butylperoxid, Kaliumperoxodiphosphat, t-Butylperoxopivalat, Cumolhydroperoxid, Isopropylbenzolmonohydroperoxid, Azobisisobutyronitril. Beispiele für monomerlösliche Initiatoren sind Dicetylperoxydicarbonat, Dicyclohexylperoxydicarbonat, Dibenzoylperoxid, tert.-Butyl-peroxyneodecanoat, tert.-Butylperoxy-2-ethylhexanoat und tert.-Butylperoxypivalat. Die genannten Initiatoren werden im allgemeinen in einer Menge von 0,01 bis 10,0 Gew.-%. bevorzugt 0,1 bis 0,5 Gew.%, jeweils bezogen auf das Gesamtgewicht der Monomere, eingesetzt, Als Redox-Initiatoren können Kombinationen aus den genannten Initiatoren mit Reduktionsmitteln verwendet werden. Geeignete Reduktionsmittel sind die Sulfite und Bisulfite der Alkalimetalle und von Ammonium, beispielsweise Natriumsulfit, die Derivate der Sulfoxylsäure, wie Zink- oder Alkaliformaldehydsulfoxylate, beispielsweise Natriumhydroxymethansulfinat, und Ascorbinsäure. Die Reduktionsmittelmenge beträgt im allgemeinen 0,01 bis 10,0 Gew.-%, bevorzugt 0,1 bis 0,5 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Monomeren.The polymerization temperature may be 40 ° C to 100 ° C, preferably 60 ° C to 90 ° C. In the copolymerization of gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride, it is also possible to work under pressure, generally between 5 bar and 100 bar. The initiation of the polymerization can be carried out with the customary water-soluble or monomer-soluble initiators or redox initiator combinations take place. Examples of water-soluble initiators are the sodium. Potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, azobisisobutyronitrile. Examples of monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate. The initiators mentioned are generally in an amount of 0.01 to 10.0 wt .-%. preferably 0.1 to 0.5 wt.%, in each case based on the total weight of the monomers, used as redox initiators, combinations of said initiators with reducing agents can be used. Suitable reducing agents are the sulfites and bisulfites of the alkali metals and of ammonium, for example sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or Alkaliformaldehydsulfoxylate, for example Natriumhydroxymethansulfinat, and ascorbic acid. The amount of reducing agent is generally from 0.01 to 10.0 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the total weight of the monomers.
Die Monomere können insgesamt vorgelegt werden, insgesamt zudosiert werden oder in Anteilen vorgelegt werden und der Rest nach der Initiierung der Polymerisation zudosiert werden. Die Dosierungen können separat (räumlich und zeitlich) durchgeführt werden oder die zu dosierenden Komponenten können alle oder teilweise voremulgiert zugegeben werden.The monomers can be submitted in total, be metered in total or be introduced in portions and the remainder be added after the initiation of the polymerization. The dosages can be carried out separately (spatially and temporally) or the components to be metered can be added all or partly pre-emulsified.
Bei den als bevorzugt genannten Verfahren der Suspension- und Emulsionspolymerisation kann in Gegenwart der vorgenannten Schutzkolloiden polymerisiert werden, um die schutzkolloidstabilisierten Polymere herzustellen.In the processes of suspension and emulsion polymerization mentioned as preferred, it is possible to polymerize in the presence of the abovementioned protective colloids in order to prepare the protective colloid-stabilized polymers.
Die vorliegende Erfindung, insbesondere in den vorstehend geschilderten bevorzugten Ausführungsformen, weist eine Vielzahl von Vorteilen auf: Zunächst ist gefunden worden, daß im Vergleich zu anderen Beschichtungsverfahren nach dem Stand der Technik sehr geringe Beschichtungsmengen für eine ausreichend gute Verklebung genügen. Dadurch ist eine deutliche Reduktion der Kosten zu erreichen, und die verklebten textilen Materialien weisen einen angenehmen weichen Griff auf. Mit den erfindungsgemäß verwendeten schutzkolloidstabilisierten Polymeren ist eine sehr hohe Haftfestigkeit der verklebten Textilien festzustellen. Die Anbindung des Streupulvers an den Unterpunkt ist sehr gut. Die Verklebungen, die mit der Beschichtung, die ein schutzkolloidstabilisiertes Polymer verwendet, erhalten wurden, sind sehr gut wasch- und reinigungsbeständig. Darüber hinaus dringt der mit dem schutzkolloidstabilisierten Polymer erhaltene Unterpunkt bei der Doppelpunktbeschichtung nicht in das textile Substrat ein, d.h. es wird eine sehr wirkungsvolle Rückschlagsperre erreicht. Des weiteren weisen Pasten, die das schutzkolloidstabilisierte Polymer enthalten und zur Herstellung des Unterpunkts bei Doppelpunktbeschichtungen verwendet werden, eine sehr gute Rheologie auf und trocknen an der Schablone nicht an.The present invention, particularly in the preferred embodiments described above, has a number of advantages. First of all, it has been found that, in comparison to other prior art coating processes, very small amounts of coating suffice for sufficiently good adhesion. As a result, a significant reduction in costs can be achieved, and the bonded textile materials have a pleasant soft touch. With the protective colloid-stabilized polymers used according to the invention, a very high adhesive strength of the bonded textiles is observed. The connection of the scattering powder to the sub-point is very good. The bonds obtained with the coating using a protective colloid-stabilized polymer are very good for washing and cleaning. In addition, the sub-point obtained with the protective colloid-stabilized polymer does not penetrate into the textile substrate during the double-point coating, ie a very effective flashback is achieved. Furthermore, pastes containing the protective colloid-stabilized polymer and to Making the subpoint used in colon coatings, has a very good rheology and does not dry on the template.
Zur Herstellung von Beschichtungen auf Trägermaterialien können die schutzkolloidstabilisierten Polymere in Form einer Paste verwendet werden. Zur Herstellung einer solchen Paste wird von einer Dispersion des schutzkolloidstabilisierten Polymers in Wasser ausgegangen. Die Menge des Wassers kann dabei beispielsweise 70 Gew.-%, bezogen auf die Dispersion, und die des schutzkolloidstabilisierten Polymers 30 Gew.-%, ebenfalls bezogen auf die Dispersion, betragen. Diesen Polymerdispersionen kann dann Verdicker und gegebenenfalls Druckhilfsmittel zugegeben werden, wodurch dann Pasten zur Beschichtung erhalten werden.For the preparation of coatings on support materials, the protective colloid-stabilized polymers can be used in the form of a paste. To prepare such a paste, a dispersion of the protective colloid-stabilized polymer in water is used. The amount of water may be, for example, 70% by weight, based on the dispersion, and that of the protective-colloid-stabilized polymer 30% by weight, likewise based on the dispersion. Thickeners and, if appropriate, printing assistants can then be added to these polymer dispersions, as a result of which pastes for coating are obtained.
Diese Pasten können beispielsweise im Rotationssiebdruck auf das zu beschichtende Trägermaterial aufgebracht werden. Auf diese Weise kann ein Unterpunkt für die Doppelpunktbeschichtung hergestellt werden. Auf den Unterpunkt kann dann Schmelzkleberpulver aufgestreut werden. Überschüssiges Pulver kann nachfolgend abgesaugt werden. Der Unterpunkt kann dann getrocknet und angesintert, oder das Streupulver aufgeschmolzen werden.These pastes can be applied, for example, in rotary screen printing on the substrate to be coated. In this way, a sub-point for the double-point coating can be produced. On the sub-point can then be sprinkled hot melt adhesive powder. Excess powder can subsequently be removed by suction. The sub-item can then be dried and sintered, or the litter powder can be melted.
Vorstehend erwähnte Polymerdispersionen haben den Vorteil, daß sie durch Zugabe von Verbindungen mit 2 oder mehr Epoxid-, Organo-, Halogen-, Hydroxy-, Aziridin-, Carbodiimid-, Oxazolin-, Alkohol-, Amin-, Aminosilan-, Aminoformaldehyd-, Isocyanat- oder N-2-Hydroxyalkylamid-Resten vemetzt werden können. Neben der intramolekularen Vernetzung des Polymeren tritt auch eine Vernetzung des Polymeren mit der Schutzkolloidhülle und mit den zugegebenen Additiven ein. Dadurch werden besonders hohe Haftfestigkeiten erreicht.The abovementioned polymer dispersions have the advantage that they are obtained by adding compounds having 2 or more epoxide, organo, halogen, hydroxyl, aziridine, carbodiimide, oxazoline, alcohol, amine, aminosilane, aminoformaldehyde, Isocyanate or N-2-hydroxyalkylamide residues can be crosslinked. In addition to the intramolecular crosslinking of the polymer, crosslinking of the polymer with the protective colloid shell and with the added additives also occurs. As a result, particularly high adhesive strengths are achieved.
In der Endformulierung der Dispersion bzw. der Paste können noch Vernetzer vorlegen, beispielsweise Verbindungen mit zwei oder mehr Epoxy-, Organo-, Halogen-, Hydroxy-, Aziridin-, Carbodiimid-, Oxazolin-, Alkohol-, Amin-, Aminosilan-, Aminoformaldehyd-, Isocyanat oder N-2-Hydroxyalkylamid-Resten.Crosslinkers may also be present in the final formulation of the dispersion or paste, for example compounds containing two or more epoxy, organo, halogen, hydroxy, aziridine, carbodiimide, oxazoline, alcohol, amine, aminosilane, Amino-formaldehyde, isocyanate or N-2-hydroxyalkylamide residues.
Bei den Trägermaterialien, die beschichtet werden können, kann es sich um Materialien jeglicher Art handeln. Es kann flexibel, wenig flexibel oder gar nicht flexibel sein. Beispiele sind textile Materialien jeglicher Art, wie Gewebe, Gewirke, Webwirkware, Raschelwaren (natürliche und synthetische. Fasern). Flies aus jeglichem Material. Des weiteren können Folien beschichtet werden, insbesondere aus Kunststoffen jeglicher Art, sowie Papier, Kunstleder, Leder, Schaumstoff und Holz.The substrates that can be coated can be materials of any kind. It can be flexible, not very flexible or not flexible at all. Examples are textile materials of any kind, such as woven, knitted, woven knitted fabric, Raschelwaren (natural and synthetic fibers). Flies made of any material. Furthermore, films can be coated, in particular of plastics of any kind, as well as paper, synthetic leather, leather, foam and wood.
Die Erfindung wird nachfolgend anhand eines Beispiels erläutert, ohne sie darauf einzuschränken.The invention will be explained below by way of example without limiting it thereto.
Herstellung einer druckfertigen Unterpunktpaste aus Polymerdispersionen ohne/mit Vemetzer
- Vergleichsdispersion 0 Selbstvernetzende Acrylat-Dispersion mit einer Glasübergangstemperatur Tg (DSC) = +2°C, die emulgatorstabilisiert ist.
- Dispersion 1 Vinylacetat/Ethylen-Dispersion mit einer Glasübergangstemperatur Tg (DSC) = +3°C, die polyvinylalkoholstabilisiert ist.
- Dispersion 2 Styrol/Butadien-Dispersion mit einer Glasübergangstemperatur Tg (DSC) = +5°C, die polyvinylalkoholstabilisiert ist.
- Dispersion 3 Acrylat-Dispersion mit einer Glasübergangstemperatur Tg (DSC) = +1°C, die polyvinylalkoholstabilisiert ist.
- Comparative Dispersion 0 Self-crosslinking acrylate dispersion having a glass transition temperature T g (DSC) = + 2 ° C., which is emulsifier-stabilized.
- Dispersion 1 Vinyl acetate / ethylene dispersion having a glass transition temperature T g (DSC) = + 3 ° C, which is polyvinyl alcohol stabilized.
- Dispersion 2 styrene / butadiene dispersion having a glass transition temperature T g (DSC) = + 5 ° C, which is polyvinyl alcohol stabilized.
- Dispersion 3 acrylate dispersion with a glass transition temperature T g (DSC) = + 1 ° C, which is polyvinyl alcohol stabilized.
Tebelink® B-IC = Polysocyanat, modifiziert, Dr. Th. Böhme KG Chem. Fabrik GmbH & Co.Tebelink® B-IC = polysocyanate, modified, Dr. med. Th. Boehme KG Chem. Fabrik GmbH & Co.
Tebelink® MFA = Partiell verethertes, modifiziertes Melamin-Formaldehyd-Kondensat, formaldehydarm (0,3%), Dr. Th. Böhme KG Chem. Fabrik GmbH & Co.
Wasser vorlegen, Acrylatverdicker einrühren, bis eine homogene, viskose Paste entstanden ist und anschließend unter Rühren die Polymerdispersion zugeben. Bei Einsatz von Vemetzern werden diese der Paste zugesetzt und homogen eingerührt.
Zur Verbesserung der Verdruckbarkeit können Druckhilfmittel wie z.B. Alkohole und hochmolekulares Polyethylenoxid zugegeben werden. Pastenviskosität je nach Beschichtungsmaschine unterschiedlich. Typische Werte liegen zwischen 7.000-15.000 m Pas, Haake Rotovisko VT02, Spindel 2.Submit water, stir in acrylate thickener until a homogeneous, viscous paste has formed and then add the polymer dispersion with stirring. When crosslinkers are used, they are added to the paste and stirred in homogeneously.
To improve the printability printing auxiliary agents such as alcohols and high molecular weight polyethylene oxide can be added. Paste viscosity varies depending on the coating machine. Typical values are between 7,000-15,000 m Pas, Haake Rotovisko VT02, spindle 2.
- Rotationssiebdruck: Schablone CP 66, Lochdurchmesser 375 µmRotary screen printing: Template CP 66, hole diameter 375 μm
- Geschwindigkeit: 10 m/min, 150°C im TrocknungskanalSpeed: 10 m / min, 150 ° C in the drying channel
- Streupulver: Copolyamid, Schmelzbereich ca. 115-125 °C, Pulver 80-160 µmScattering powder: copolyamide, melting range approx. 115-125 ° C, powder 80-160 μm
- 2 Substrate: Standard-Vlies (100% PES), Gewebe (100% PES, stark hydrophobiert, elastisch)2 substrates: standard non-woven (100% PES), fabric (100% PES, highly hydrophobic, elastic)
Laminierpresse Fa. Mayer
Kaschierbedingungen: 127°C Fugentemperatur, Durchlaufgeschwindigkeit 6 m/min, Fixierzeit:
10.5 s, Fixierdruck: 4 Bar
Kaschiermaterial: 55% Polyester/45% Wolle
Laminating press Fa. Mayer
Laminating conditions: 127 ° C joint temperature, flow rate 6 m / min, fixing time:
10.5 s, fixing pressure: 4 bar
Lining material: 55% polyester / 45% wool
Claims (17)
- Use of a protective colloid-stabilised polymer, including a protective colloid and a polymer for coating a substrate liner wherein the coating is a double dot coating.
- Use according to claim 1, whereby the protective colloid is selected from modified natural polymers, synthetic homo- and co-polymers, graft polymers and condensation products.
- Use according to one of the preceding claims whereby the polymer can be produced from at least one ethylenically unsaturated monomer which is selected from vinyl esters of unbranched or branched alkyl carbonic acids with 1 to 18 C atoms, acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 C atoms, C2-C20 mono or dicarbonic acids, amides thereof, N-methylolamides or nitriles, C2-C20 sulphonic acids, 3-20 element heterocyclic compounds with oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, boron and aluminium as heteroatom, dienes with at least 4 C atoms, olefins with at least 2 C atoms, vinyl aromatics and C2-C20 vinyl halides
- Use according to claim 3 whereby the vinyl ester is selected from vinyl acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl ester of α-branched monocarbonic acids with 9 to 13 C atoms.
- Use according to claim 3 whereby the acrylic acid or methacrylic acid ester is selected from methylacrylate, methyl methacrylate, ethylacrylate, ethyl methacrylate, propylacrylate, propyl methacrylate, n-butylacrylate, n-butyl methacrylate, t-butylacrylate, t-butyl methacrylate, 2-ethyl hexylacrylate.
- Use according to claim 3 whereby the mono and dicarbonic acids, amides thereof, n-methylolamides and nitriles are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide, N-methylolacrylamide, N-methylolmethacrylamide and acrylonitrile.
- Use according to claim 3 whereby the sulphonic acid is selected from vinyl sulphonic acid and 2-acrylamido-2-methyl-propanesulphonic acid.
- Use according to claim 3 whereby the heterocyclic compound is selected from vinyl pyrrolidone and vinyl pyridine.
- Use according to claim 3 whereby the vinyl aromatic is selected from styrene, methyl styrene and vinyl toluene.
- Use according to claim 3 whereby the vinyl halide is vinyl chloride.
- Use according to claim 3, whereby the olefin is selected from ethylene and propylene.
- Use according to claim 3, whereby the diene is selected from 1,3-butadiene and isoprene.
- Use according to one of the preceding claims, whereby in addition to the monomer a comonomer is used in a quantity of 0.1 to 50 % by weight in relation to the total weight of the polymer for manufacture of the polymer.
- Use according to one of the preceding claims, whereby the polymer has a glass transition temperature Tg of -50°C to 120°C.
- Use according to one of the preceding claims, whereby the protective colloid-stabilised polymer is present in the form of an aqueous dispersion.
- Use according to one of the preceding claims, whereby the protective colloid-stabilised polymer is present in the form of a paste.
- Use according to one of the preceding claims, whereby the coating is carried out by means of rotary screen printing.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES03028481T ES2259747T3 (en) | 2003-12-12 | 2003-12-12 | USE OF POLYMERS STABILIZED WITH PROTECTIVE COLOIDS FOR COATING BY DOUBLE POINTS. |
| AT03028481T ATE321909T1 (en) | 2003-12-12 | 2003-12-12 | USE OF PROTECTIVE COLLOID-STABILIZED POLYMERS FOR DOUBLE POINT COATINGS |
| DE50302798T DE50302798D1 (en) | 2003-12-12 | 2003-12-12 | Use of protective colloid-stabilized polymers for double-point coatings |
| EP03028481A EP1541751B1 (en) | 2003-12-12 | 2003-12-12 | Use of protective colloid-stabilized polymers as double-point coatings |
| PCT/EP2004/013642 WO2005059238A1 (en) | 2003-12-12 | 2004-12-01 | Use of protective colloid-stabilized polymers for double-point coatings |
| KR1020067011386A KR20060121165A (en) | 2003-12-12 | 2004-12-01 | How to use protective colloid stabilized polymer for double dot coating |
| US10/582,072 US20070128362A1 (en) | 2003-12-12 | 2004-12-01 | Use of protective colloids-stabilized polymers for double dot coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03028481A EP1541751B1 (en) | 2003-12-12 | 2003-12-12 | Use of protective colloid-stabilized polymers as double-point coatings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1541751A1 EP1541751A1 (en) | 2005-06-15 |
| EP1541751B1 true EP1541751B1 (en) | 2006-03-29 |
Family
ID=34486184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03028481A Expired - Lifetime EP1541751B1 (en) | 2003-12-12 | 2003-12-12 | Use of protective colloid-stabilized polymers as double-point coatings |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20070128362A1 (en) |
| EP (1) | EP1541751B1 (en) |
| KR (1) | KR20060121165A (en) |
| AT (1) | ATE321909T1 (en) |
| DE (1) | DE50302798D1 (en) |
| ES (1) | ES2259747T3 (en) |
| WO (1) | WO2005059238A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2703353A1 (en) | 2007-10-25 | 2009-04-30 | Kufner Textil Gmbh | Heat-sealable, plannar textile structure, production and use thereof |
| DE102009001818A1 (en) * | 2009-03-24 | 2010-09-30 | Wacker Chemie Ag | Use of protective colloid-stabilized polymers as low-profile additives (LPA) |
| DE102018214839B4 (en) | 2018-08-31 | 2021-05-12 | Kufner Holding Gmbh | Heat-sealable, textile fabric with a sustainable adhesive coating and its use |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1197570A (en) * | 1966-11-21 | 1970-07-08 | Courtaulds Ltd | Adhesive Compositions |
| US3632535A (en) * | 1967-09-20 | 1972-01-04 | Cpc International Inc | Emulsion polymerization method and resultant aqueous latex |
| DE2407505B2 (en) * | 1974-02-16 | 1979-05-23 | Plate Bonn Gmbh, 5300 Bonn | Aqueous plastic powder dispersion and its use for heat sealing textiles, leather or furs |
| DE3510109C2 (en) * | 1985-03-20 | 1987-04-30 | Dr. Th.Böhme KG Chem. Fabrik GmbH & Co, 8192 Geretsried | Suspending agent and its use |
| EP0373231A1 (en) * | 1988-12-12 | 1990-06-20 | KUFNER TEXTILWERKE GmbH | Method of screen coating plastic sheets with hot melt adhesives, and use of the coated sheets |
| JPH04178476A (en) * | 1990-11-13 | 1992-06-25 | Cemedine Co Ltd | Coating agent for preventing cargo shifting of paper container and anti-slip corrugated board case coated with the agent |
| ES2078418T3 (en) * | 1991-12-17 | 1995-12-16 | Kufner Textilwerke Gmbh | COATED SURFACE PRINT. |
| DE4313206A1 (en) * | 1993-04-22 | 1994-10-27 | Wacker Chemie Gmbh | Use of aqueous vinyl ester copolymer dispersions as adhesives, which are easy to wash off during processing, but form waterproof bonds |
| DE4407842A1 (en) * | 1994-03-09 | 1995-09-14 | Huels Chemische Werke Ag | Protective colloid-stabilized polyacrylate dispersions |
| EP0965598A1 (en) * | 1998-06-17 | 1999-12-22 | Hercules Incorporated | New protective colloids in latices with improved film formation at low temperatures |
-
2003
- 2003-12-12 EP EP03028481A patent/EP1541751B1/en not_active Expired - Lifetime
- 2003-12-12 ES ES03028481T patent/ES2259747T3/en not_active Expired - Lifetime
- 2003-12-12 DE DE50302798T patent/DE50302798D1/en not_active Expired - Fee Related
- 2003-12-12 AT AT03028481T patent/ATE321909T1/en not_active IP Right Cessation
-
2004
- 2004-12-01 US US10/582,072 patent/US20070128362A1/en not_active Abandoned
- 2004-12-01 KR KR1020067011386A patent/KR20060121165A/en not_active Application Discontinuation
- 2004-12-01 WO PCT/EP2004/013642 patent/WO2005059238A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060121165A (en) | 2006-11-28 |
| ATE321909T1 (en) | 2006-04-15 |
| DE50302798D1 (en) | 2006-05-18 |
| WO2005059238A1 (en) | 2005-06-30 |
| US20070128362A1 (en) | 2007-06-07 |
| EP1541751A1 (en) | 2005-06-15 |
| ES2259747T3 (en) | 2006-10-16 |
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