EP1984557A2 - Method for treating polypropylene textiles - Google Patents
Method for treating polypropylene textilesInfo
- Publication number
- EP1984557A2 EP1984557A2 EP07704213A EP07704213A EP1984557A2 EP 1984557 A2 EP1984557 A2 EP 1984557A2 EP 07704213 A EP07704213 A EP 07704213A EP 07704213 A EP07704213 A EP 07704213A EP 1984557 A2 EP1984557 A2 EP 1984557A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polypropylene
- butyl
- ethylene
- aqueous formulation
- ethylenically unsaturated
- 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.)
- Withdrawn
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 87
- 239000004753 textile Substances 0.000 title claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 48
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000013011 aqueous formulation Substances 0.000 claims abstract description 27
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 40
- 229920001296 polysiloxane Polymers 0.000 claims description 37
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 239000004566 building material Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229910014033 C-OH Inorganic materials 0.000 claims description 5
- 229910014570 C—OH Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000004746 geotextile Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000012874 anionic emulsifier Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims 1
- 239000012875 nonionic emulsifier Substances 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 15
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 14
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 7
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- BXYVQNNEFZOBOZ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n',n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCNCCCN(C)C BXYVQNNEFZOBOZ-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 210000003632 microfilament Anatomy 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 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
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical class CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- ADNTWSHRSHPGHG-UHFFFAOYSA-N 1,3-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC(C(C)C)=C1 ADNTWSHRSHPGHG-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- MLFIYYDKLNZLAO-UHFFFAOYSA-N 2-aminoethane-1,1-diol Chemical compound NCC(O)O MLFIYYDKLNZLAO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-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
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- WLUBWHFAHMHXCM-UHFFFAOYSA-N CC[N+](C)([O-])O Chemical compound CC[N+](C)([O-])O WLUBWHFAHMHXCM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- VVAOPCKKNIUEEU-UHFFFAOYSA-L cycloocta-1,5-diene;platinum(2+);dichloride Chemical compound Cl[Pt]Cl.C1CC=CCCC=C1 VVAOPCKKNIUEEU-UHFFFAOYSA-L 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZUXWMZPBQLGDDY-UHFFFAOYSA-N n,n-dihydroxyethanamine Chemical compound CCN(O)O ZUXWMZPBQLGDDY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- KXYJPVZMZBJJBZ-UHFFFAOYSA-N tert-butyl 2-ethylbutaneperoxoate Chemical compound CCC(CC)C(=O)OOC(C)(C)C KXYJPVZMZBJJBZ-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
- VSJBBIJIXZVVLQ-UHFFFAOYSA-N tert-butyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(C)(C)C VSJBBIJIXZVVLQ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6433—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing carboxylic groups
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
Definitions
- the present invention relates to a process for treating textiles made of polypropylene, which is characterized in that it is treated with an emulsifier-free aqueous formulation containing
- the present invention relates to textiles made of polypropylene, treated by the method according to the invention, and their use. Furthermore, the present invention relates to aqueous formulations containing
- the present invention relates to the use of silicone compounds having at least one NH group or at least one alkylene oxide unit for the hydrophilization of textiles made of polypropylene.
- the inventive method is based on textiles made of polypropylene, wherein also those textiles are included, which consist of polypropylene and at least one other material, for example mixtures of polypropylene and cotton or polyester.
- polypropylene is understood to mean not only homopolymers of propylene, but also those copolymers of propylene which contain one or more olefins, preferably ⁇ -olefins such as, for example, 1-butene or 1-hexene or ethylene in copolymerized form.
- Copolymers of propylene are preferably those copolymers in which at least 50% by weight of the copolymerized comonomers are propylene, more preferably at least 70% by weight.
- Polypropylene in the context of the present invention is preferably isotactic.
- textiles are preferably thread-like, i. linear structures, for example threads, fibers, filaments, microfilaments, microfibers, monofilaments, multifilaments, staple fibers, in each case textured or untextured.
- textiles may, however, also be flat structures or planar structures made of polypropylene, which are preferably obtainable by combining a plurality of thread-like structures made of polypropylene, for example nonwovens, woven fabrics, knitted fabrics, knitted fabrics, scrims and mixtures, and which may be made using other also thread-like structures, such as synthetic fibers such.
- polyamide, polyethylene len, polyester or acrylic, or natural fibers such as cotton are preferably sheet-like structures or fibers or filaments which are produced either from polypropylene or from mixtures of polyethylene and polypropylene.
- the textile of polypropylene to be treated is not pretreated separately before the treatment according to the invention, that is to say it is neither hydrophilized nor hydrophobized.
- textile to be treated is neither pretreated by plasma treatment nor by, for example, lightning discharges.
- textile is treated from propylene with an emulsifier-free aqueous formulation.
- Treating is understood as meaning, for example, soaking, spraying, kiss-roll application and, in particular, padding. According to the invention, it is treated several times or preferably only once.
- textile is treated from polypropylene with an emulsifier-free aqueous formulation.
- an aqueous formulation with which textile is treated from polypropylene does not add a low molecular weight emulsifier, ie no emulsifiers having molecular weights of up to 400 g / mol, in one embodiment no emulsifiers having molecular weights of up to 500 g / mol.
- M n is considered.
- emulsifiers are surface-active anionic, cationic or nonionic compounds, for example quaternary ammonium salts of Cs-C4o fatty amines, C8-C4o-fatty alcohol sulfates, C8-C4o-fatty alcohol phosphates, C8-C4o-fatty alcohol sulfonates, C8- C4o-fatty alcohol phosphonates, sulfonates of Cs-Cao-alkylaromatics, with C ⁇ -CUo fatty alcohol alkoxylated in the range from 15 to 150 equivalents of alkylene oxide, for example ethylene oxide or propylene oxide.
- alkylene oxide for example ethylene oxide or propylene oxide.
- emulsifier-free is understood as meaning that a total of less than 0.1% by weight of emulsifier characterized above is in the aqueous formulation used in the process according to the invention, preferably 0.001 to 0.01% by weight. %, based on the respective aqueous formulation.
- Aqueous formulation used in the process according to the invention comprises (a) at least one silicone compound having at least one hydrophilic group, also referred to as silicone compound (a) in the context of the present invention, or
- Silicone compounds (a) are preferably those compounds which are made up of a plurality of Si (R 1 ) (R 2 ) -O units, so that Si-O chains are formed and terminally with either OH groups or are saturated with further radicals R 1 .
- the radicals R 1 and R 2 may be the same or a majority of the same and are mainly selected from C 6 -C 14 -aryl, in particular phenyl, or C 1 -C 4 -alkyl, preferably unbranched, and in particular methyl.
- Silicone compound (a) carries at least one hydrophilic group, which may be located, for example, on one of the terminal or, if present, one of the middle Si atoms of the Si-O chains described above. In one embodiment of the present invention, silicone compound (a) may have two or three hydrophilic groups per molecule, which may be different or preferably the same.
- the hydrophilic group or groups are connected via a spacer to one of the terminal or, if present, one of the middle Si atoms of the above-described Si-O chains, for example a C 2 -C 2 oxide.
- Alkylene spacer which may be branched or preferably unbranched and in which one or more non-adjacent CH 2 groups may be replaced by oxygen atoms.
- silicone compound (a) has a kinematic viscosity in the range of 100 to 100,000 m 2 / s, determined at 23 ° C.
- silicone compound (a) is a silicone compound having at least one NH group or at least one C-OH group or at least one alkylene oxide unit per molecule.
- silicone compound (a) may have at least one NH group.
- NH groups are NH (C 1 -C 10 -alkyl) groups, in particular NH-methyl, NH-ethyl, NH (C 6 -C 4 -aryl) groups, in particular NH (C 6 H 5 ), NH ( C 7 -C 20 aralkyl) groups, in particular NH-benzyl, NH (C 7 -C 20 -alkylaryl) groups, in particular NH- (para-tolyl), NH 2 groups, NH-CH 2 -CH 2 -NH 2 , -CONH 2 , NH- (CH 2 ) 3 -NH 2 .
- silicone compound (a) may have at least one C-OH group, which may be, for example, an alcoholic OH group or a COOH group.
- at least one C-OH group in silicone compound (a) is a secondary or more preferably a primary C-OH group, for example a CH 2 -OH group, a CH 2 -CH 2 -OH Group or a CH 2 -CH 2 -CH 2 -OH group.
- silicone compound (a) may have at least one alkylene oxide unit per molecule, preferably at least 3 to 20 alkylene oxide units per molecule. Examples of alkylene oxide units are C 2 -C 6 -alkylene oxide units, for example propylene oxide units or butylene oxide units or preferably ethylene oxide units.
- silicone compound (a) may be at least one compound obtained by reacting an excess of such silicone having at least one Si-H group per molecule, preferably at least two Si-H groups per Molecule, in the presence of a Pt-based catalyst with at least one compound of general formula I,
- R 3 is selected from C 1 -C 6 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert -butyl;
- C 2 -C 6 alkenyl for example vinyl, 1-allyl, 2-allyl, 3-allyl, homoallyl, ⁇ -hexenyl, ⁇ -pentenyl and preferably vinyl or 3-allyl,
- R 4 is the same or different and is independently selected from ethyl, methyl and in particular hydrogen,
- a 1 , A 2 different or preferably the same and selected from NH, O,
- n is an integer in the range of 1 to 100, preferably 2 to 50.
- Suitable Pt-based catalysts are, for example, PtCl 4 , H 2 PtCl 6 .6H 2 O, platinum-olefin complexes, finely divided silica gel or activated carbon or platinum supported on alumina or complexes of Pt with ethers, aldehydes, ketones, alcoholates, for example norbornadiene-platinum dichloride or 1,5-Cyclooctadiene platinum dichloride.
- silicone compounds (a) obtainable by reacting the abovementioned silicone compound with one or more diisocyanates, preferably with one or more aliphatic or cycloaliphatic diisocyanates, for example 4,4'-methylene-dicyclohexyldiisocyanate , Dodecamethylene diisocyanate, tetramethylene diisocyanate and especially hexamethylene diisocyanate (HDI) and isophorone diisocyanate.
- diisocyanates are aromatic diisocyanates such as 2,4-TDI, 2,6-TDI (tolylene diisocyanate).
- silicone compounds (a) obtainable by reacting the abovementioned silicone compound with one or more aliphatic, aromatic or cycloaliphatic diisocyanates and one or more diols, triols, diamines, triamines or polyamines is, in particular aliphatic diols, triols, diamines, triamines or polyamines such as bis (dimethylaminopropyl) amine.
- diols are amino diols such as N-methyldiethanolamine, diethanolamine, N- (n-butyl) diethanolamine.
- Silicone compounds of the aforementioned type and their preparation are described, for example, in WO 05/121218.
- An aqueous formulation used in the process according to the invention may contain at least one ethylene copolymer (b).
- ethylene copolymer (b) contains in copolymerized form:
- At least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula II
- R 5 is selected from hydrogen
- C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; especially preferred are C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- R 6 is selected from hydrogen
- C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-
- R 5 is methyl or hydrogen and R 6 is hydrogen.
- Particularly suitable anhydrides of ethylenically unsaturated carboxylic acids are maleic anhydride and itaconic anhydride.
- Ethylene copolymer (b) may contain one or more further comonomers in copolymerized form, specifically up to 40% by weight, preferably up to 35% by weight, based in each case on the sum of ethylene and copolymerized or copolymerized ethylenically unsaturated carboxylic acid (s). , for example, it may be copolymerized: vinyl acetate, one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula III
- R 7 is selected from C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
- R 8 is selected from hydrogen
- C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; special C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
- R 9 selected from hydrogen, Ci-Cio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; COOH 1 COOCH 31 COOC 2 H 5 .
- R 8 is hydrogen or methyl and R 9 is hydrogen.
- R 8 is hydrogen or methyl and R 9 is hydrogen and R 7 is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.
- Ethylene copolymer (b) can be advantageously prepared by free-radically initiated copolymerization under high-pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred.
- High pressure autoclaves are known per se, a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. With them predominantly the ratio length / diameter at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1 behaves.
- Suitable pressure conditions for the copolymerization are 500 to 4000 bar, preferably 1500 to 2500 bar.
- the reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 200 to 280 ° C.
- the copolymerization can be carried out in the presence of a regulator.
- the regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula III
- radicals R 8 are identical or, in particular in the case of aldehydes, different and selected from hydrogen;
- C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo Pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably Ci-C 4 -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl, sec-butyl and tert.
- Ci-C 4 -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl, sec-butyl and ter
- C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
- the R 8 groups are covalently linked together to form a 4- to 13-membered ring.
- both radicals R 8 may be common: - (CHa) 4 -, - (CHb) S-, - (CH 2 ) 6, - (CH 2 ) 7 -, -CH (CHa) -CH 2 -CH 2 -CH (CH 3 ) - or -CH (CHa) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
- radical initiators for the radical copolymerization the usual radical initiators such as organic peroxides, oxygen or azo compounds can be used. Also mixtures of several radical starters are suitable.
- Suitable peroxides selected from the commercially available substances are didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2 ethyl hexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxydiethyl isobutyrate, 1,4-di (tert-butyl peroxycarbonyl) cyclohexane as isomer mixture, tert-butyl perisononanoate 1, 1-di- (tert-butyl-peroxy ) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, methyl isobutyl ketone
- tert-butyl peroxybenzoate di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, tert-butyl cumyl peroxide, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or dimeric or trimeric ketone peroxides, as are known from EP-A 0 813 550.
- di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisone nonanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable.
- azo compound azobisisobutyronitrile ("AIBN") is mentioned as an example Radical starters are metered in amounts customary for polymerizations.
- AIBN azobisisobutyronitrile
- Radical starters are metered in amounts customary for polymerizations.
- Many commercially available organic peroxides are added to so-called phlegmatizers before they are sold to make them more manageable.
- white oil or hydrocarbons, in particular isododecane are suitable as phlegmatizers.
- ethylene copolymers (b) have a melt flow rate (MFR) in the range of 1 to 500 g / 10 min, preferably 5 to 200 g / 10 min, more preferably 7 to 50 g / 10 min, measured at 160 ° C and a load of 325 g according to DIN 53735.
- MFR melt flow rate
- ethylene copolymers (b) have a kinematic melt viscosity v in the range of 500 to 10,000 mm 2 / s, preferably in the range of 800 to 4,000 mm 2 / s, measured according to DIN 51562.
- the density of ethylene copolymer (b) is from 0.89 to 1.10 g / cm 3 , preferably from 0.92 to 0.94 g / cm 3 , determined according to DIN 53479.
- Ethylene copolymer (b) may be an alternating copolymer or a block copolymer or preferably a random copolymer.
- Ethylene copolymer (b) can be present as free acid with respect to copolymerized ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated C 4 -C 10 -dicarboxylic acid or be partially or completely neutralized, for example with alkali metal such as. As sodium or potassium or with alkaline earth metal such as magnesium or calcium or with ammonia or organic amine, in particular C 1 -C 4 monoalkylamine, di-C 1 -C 4 -alkylamine, tri-C 1 -C 4 -alkylamine or tetra-C 1 -C 4 be neutralized alkylammonium. If desired, copolymerized anhydride of ethylenically unsaturated C 4 -C 10 -dicarboxylic acid may also be present in hydrolyzed form.
- x is an integer in the range of zero to three, preferably zero or one
- y is an integer in the range of one to four, with the proviso that the sum of x and y does not exceed four.
- Preferred examples of C 1 -C 4 - ⁇ -hydroxyalkyl are 3-hydroxypropyl, 4-hydroxybutyl and in particular 2-hydroxyethyl, also referred to below as hydroxyethyl.
- hydroxyalkylammonium are N, N-dihydroxyethylammonium, N-methyl-N-hydroxyethylammonium, N, N-dimethyl-N-hydroxyethylammonium, N-methyl-N, N-dihydroxyethylammonium, Nn-butyl-hydroxyethylammonium ammonium, Nn-butyl-N, N-dihydroxyethylammonium.
- organic amines for neutralizing are, for example, morphine-Nn, imidazole, N4-amines, imidazolines, oxazolines, triazoles and fatty acid alkanolamines.
- Suitable neutralizing agents are furthermore KOH, NaOH, Ca (OH) 2, NaHCO 3, Na 2 CO 3 , K 2 CO 3 and KHCO 3 .
- aqueous formulations used in the process according to the invention preferably have a basic pH, for example pH values from 7.5 to 14, preferably from 8 or higher and particularly preferably from 8.5 or higher.
- polypropylene fabric may be treated at a temperature in the range of 0 ° C to 145 ° C, preferably up to 130 ° C. If you want to treat at temperatures in the range of 100 to 145 ° C, so you have to treat at a pressure that is above normal pressure. If you want to work at temperatures in the range of 0 to 100 ° C, then normal pressure is suitable.
- polypropylene fabric is treated with an aqueous formulation, which may also be referred to as an aqueous liquor.
- an aqueous formulation which may also be referred to as an aqueous liquor.
- the liquor pickup can be selected such that a liquor uptake of 25% by weight to 95% by weight is preferred by the process according to the invention 60 to 90 wt .-% results.
- the method according to the invention is carried out in conventional machines used for finishing textiles, for example foulards.
- foulards Preference is given to foulards with vertical textile draw, which contain as an essential element two rollers pressed against one another, through which the textile is guided out of polypropylene.
- aqueous formulation is preferably filled in and wets the textile made of polypropylene. The pressure squeezes off the textile made of polypropylene and ensures a constant application.
- textile is made of polypropylene. pass through an immersion bath and then upwards through two rollers pressed onto each other. In the latter case one speaks also of foulards with vertical Textileinzug from below. Foulards are described, for example, in Hans-Karl Rouette, "Handbuch der Textilveredlung", Deutscher fraverlag 2003, p. 618-620.
- the process according to the invention can be carried out in the manner of an exhaust process, for example by spraying, patting, kiss-rolling or by printing.
- the process according to the invention is carried out in the manner of an exhaust process, with a liquor pick-up in the range from 1 to 50%, preferably from 20 to 40%.
- polypropylene following the treatment of textile, may be thermally treated, for example by drying at temperatures in the range of 30 to 100 ° C or by thermal fixing at temperatures in the range of at least 100, preferably at least 101 ° C. up to 150 ° C, preferably up to 135 ° C.
- two thermal treatment steps are carried out at different temperatures, for example drying in a first step at temperatures in the range of 30 to 100 ° C over a period of 10 seconds to 20 minutes, and then fixed at Temperatures in the range of 101 to 135 ° C over a period of 30 seconds to 3 minutes.
- the aqueous formulation used in the process according to the invention may contain at least one silicone compound (a) and at least one ethylene copolymer (b).
- aqueous formulation used in the process according to the invention may contain one or more additives (d).
- Suitable additives (d) are, for example, organic solvents, organic solvents such as dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethylene glycol, diethylene glycol, butyl glycol, dibutyl glycol, and, for example, residual alcohol-free alkoxylated n- C4-C6-alkanol, preferably residual alcohol-free one to 10-fold, particularly preferably 3- to 6-fold ethoxylated n-C4-C6-alkanol.
- residual alcohol is to be understood as meaning the respectively non-alkoxylated n-C4-C6-alkanol.
- Another object of the present invention are aqueous formulations containing
- Silicone compound (a) and ethylene copolymer (b) are described above.
- aqueous formulation according to the invention comprises:
- the aqueous formulation according to the invention contains no colorants such as, for example, pigments, dyes or disperse dyes.
- Aqueous formulation according to the invention may contain from zero to a total of 5% by weight of additives, preferably from 0.5 to 3.5% by weight, based on the total aqueous formulation according to the invention.
- Another object of the present invention are textiles made of polypropylene, treated by the method according to the invention. Textiles of the invention show a good and generally durable hydrophilicity, which can be detected, for example, by determining the sinking depth of a drop of water. Furthermore, in the case of such textiles of polypropylene according to the invention, which are used as or for the production of clothing, an improved trac comfort is observed.
- polypropylene textiles according to the invention comprise 0.1% by weight 0 to 5% by weight, preferably 0.5% by weight 0 to 3% by weight of silicone compound (a) or 0.1% by weight % to 5% by weight, preferably 0.5% to 0% to 3% by weight of ethylene copolymer (b).
- Polypropylene textiles according to the invention can be used, for example, advantageously as hygiene fleeces, as fire-retardants for building materials such as, for example, mortar or concrete, as a constituent of sportswear, underwear, safety clothing or filters.
- building materials such as mortar or concrete in particular containing at least one inventive textile made of polypropylene, preferably in the form of microfibers or microfilaments.
- textiles according to the invention are excellently distributed, and the connection is good.
- building materials according to the invention, built into structures such as buildings tend not to burst so much at high temperatures.
- building materials containing at least one textile according to the invention it is possible to proceed, for example, by introducing and mixing in textile according to the invention in conventional building material such as, for example, concrete or mortar.
- conventional building material such as, for example, concrete or mortar.
- building material according to the invention such as concrete according to the invention, according to methods known per se, or to apply building material according to the invention, in particular mortar according to the invention, by methods known per se.
- a further subject of the present invention are hygiene mats, for example for diapers or sanitary napkins, produced using textile according to the invention.
- Foulard Manufacturer Fa. Mathis, type no. HVF12085, contact pressure 1 - 3 bar. The contact pressure was always set so that the liquor pick-up (based on the weight of the goods) was 70 to 100%. The fleet had room temperature, unless stated otherwise. Dryer / Fixer: continuous dryer of the company Mathis THN 12589 The sinking time was determined by the TEGEWA ear test.
- n 1 ° mixed with a water content of 686 ppm by weight and heated to 100 ° C. Thereafter, 0.14 g of a (based on elemental platinum) 2.7 wt .-% solution of a Pt-1, 3-divinyl-1,1,3,3-tetramethyldisiloxan complex in ⁇ , ⁇ -Divinylpolydimethylsiloxan with a dynamic Viscosity of 1000 mPa-s added, determined at 25 ° C. The temperature rose by about 19 ° C, and there was a clear product. The mixture was stirred for one hour at 100 to 1 10 ° C, then the conversion of Si-bonded hydrogen was complete.
- a fabric (100% polypropylene, 150 g / m 2 basis weight) was padded with an aqueous formulation consisting of
- the sink-in time for one drop of distilled water was 8 seconds (untreated fabric) or less than 0.5 seconds (fabric T1 according to the invention). 11.1 Production of Textile T2 According to the Invention
- the fleet intake is about 70%. It was then dried at 100 ° C for 5 minutes, then fixed at 1 10 ° C for 1 minute. Inventive textile T2 was obtained.
- the sink-in time for a water drop was> 30 seconds (untreated textile) or ⁇ 0.5 seconds (textile T2 according to the invention).
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Abstract
The invention relates to a method for treating polypropylene textiles, which is characterised in that said textiles are treated with an emulsifier-free aqueous formulation which contains: a) at least one silicon compound having at least one hydrophilic group or b) at least one ethylene copolymer which is obtained by copolymersing ethylene with at least one ethylenically unsaturated mono or dicarboxylic acid or an anhybrid of an ethylenically unsaturated mono or dicarboxylic acid.
Description
Verfahren zur Behandlung von Textilien aus PolypropylenProcess for the treatment of textiles made of polypropylene
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zum Behandeln von Textilien aus Polypropylen, das dadurch gekennzeichnet ist, dass man sie mit einer Emulgator-freien wässrigen Formulierung behandelt, die enthältThe present invention relates to a process for treating textiles made of polypropylene, which is characterized in that it is treated with an emulsifier-free aqueous formulation containing
(a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe oder(a) at least one silicone compound having at least one hydrophilic group or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or dicarboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid.
Weiterhin betrifft die vorliegende Erfindung Textilien aus Polypropylen, behandelt nach dem erfindungsgemäßen Verfahren, und ihre Verwendung. Weiterhin betrifft die vorlie- gende Erfindung wässrige Formulierungen, enthaltendFurthermore, the present invention relates to textiles made of polypropylene, treated by the method according to the invention, and their use. Furthermore, the present invention relates to aqueous formulations containing
(a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe oder(a) at least one silicone compound having at least one hydrophilic group or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or dicarboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid.
Weiterhin betrifft die vorliegende Erfindung die Verwendung von Silikonverbindungen mit mindestens einer NH-Gruppe oder mindestens einer Alkylenoxideinheit zum Hyd- rophilieren von Textilien aus Polypropylen.Furthermore, the present invention relates to the use of silicone compounds having at least one NH group or at least one alkylene oxide unit for the hydrophilization of textiles made of polypropylene.
Polypropylen als inhärent bakterienfeindliches und kostengünstiges Material zur Herstellung von Textilien wie beispielsweise Fasern und Flächengebilden, insbesondere Fasermaterial, wird in vielen Funktionstextilien eingesetzt, z.B. in Windelvliesen und als Zuschlag für Beton zum Brandschutz. Bei der Brandschutzausrüstung von Beton wird ausgenutzt, dass Polypropylen bei Temperaturen oberhalb von 200°C depolymerisiert und gasförmiges Propylen entsteht, das schnell entweicht. Dadurch bilden sich Kanäle, durch die Wasser, das im Brandfall bei ca. 300°C zum explosiven Zerplatzen des Betonkörpers führt, entweichen kann.Polypropylene as inherently hostile to bacteria and inexpensive material for the production of textiles such as fibers and fabrics, especially fiber material, is used in many functional textiles, e.g. in diaper fleeces and as a supplement for concrete for fire protection. In the fire protection equipment of concrete is exploited that polypropylene depolymerises at temperatures above 200 ° C and gaseous propylene is formed, which escapes quickly. This creates channels through which water, which leads to explosive bursting of the concrete body in the event of fire at approx. 300 ° C, can escape.
In vielen der vorstehend genannten Anwendungen ist die Hydrophobie von Polypropy- len unerwünscht. Daher wird z. B. Polypropylen für die Windelherstellung durch eine oberflächenaktive, schwer wasserlösliche Substanz hydrophiliert (hydrophil ausgerüstet). Die im Gebrauch abgelösten geringen Mengen dieser oberflächenaktiven Stoffe bergen die Gefahr von Hautirritationen.In many of the applications mentioned above, the hydrophobicity of polypropylene is undesirable. Therefore, z. B. polypropylene for diaper production by a surface-active, poorly water-soluble substance hydrophilic (hydrophilic equipped). The small amounts of these surface-active substances released in use harbor the risk of skin irritation.
Die vorstehend genannte fehlende Permanenz der hydrophilen Ausrüstung ist auch der Grund, weshalb heute immer noch die gleichmäßige Verteilung von Polypropylen im Beton eine große Herausforderung ist. Eine Plasmabehandlung wäre für Polypropylen-
fasern zwar möglich, allerdings ist es schwer, über einen größeren Zeitraum, beispielsweise von Tagen, eine zufrieden stellende Hydrophilie der Polypropylen- Faseroberfläche zu stabilisieren.The aforementioned lack of permanence of the hydrophilic finish is also the reason why the even distribution of polypropylene in concrete is still a big challenge today. A plasma treatment would be for polypropylene Although fibers are possible, however, it is difficult to stabilize a satisfactory hydrophilicity of the polypropylene fiber surface over a relatively long period, for example of days.
Es bestand also die Aufgabe, ein Verfahren bereit zu stellen, durch das sich PoIy- proyplen einfach und möglichst dauerhaft hydrophil behandeln lässt und das nach Möglichkeit und Erfordernis oben bezeichnete Nachteile wie beispielsweise potenzielle Hautirritationen vermeidet. Weiterhin bestand die Aufgabe, Formulierungen bereit zu stellen, mit deren Hilfe sich Polyproyplen einfach und möglichst dauerhaft hydrophil behandeln lässt. Weiterhin bestand die Aufgabe, hydrophiliertes Polypropylen bereit zu stellen.It was therefore the object to provide a method by which polypropyls can be treated simply and as permanently as possible hydrophilic and avoids the disadvantages and potentials mentioned above, such as potential skin irritations. A further object was to provide formulations with which polyproplene can be treated simply and as permanently as possible hydrophilic. Another object was to provide hydrophilic polypropylene.
Demgemäß wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.
Das erfindungsgemäße Verfahren geht aus von Textilien aus Polypropylen, wobei auch solche Textilien mit umfasst sind, die aus Polypropylen und mindestens einem weiteren Material bestehen, beispielsweise Mischungen aus Polypropylen und Baumwolle oder Polyester. Unter Polypropylen werden im Zusammenhang mit der vorliegenden Erfindung nicht nur Homopolymere des Propylens verstanden, sondern auch solche Copo- lymere des Propylens, die ein oder mehrere Olefine, bevorzugt α-Olefine wie beispielsweise 1 -Buten oder 1 -Hexen oder Ethylen einpolymerisiert enthalten. Vorzugsweise handelt es sich bei Copolymeren des Propylens um solche Copolymere, bei denen mindestens 50 Gew.-% der einpolymerisierten Comonomere Propylen sind, besonders bevorzugt mindestens 70 Gew.-%.The inventive method is based on textiles made of polypropylene, wherein also those textiles are included, which consist of polypropylene and at least one other material, for example mixtures of polypropylene and cotton or polyester. In the context of the present invention, polypropylene is understood to mean not only homopolymers of propylene, but also those copolymers of propylene which contain one or more olefins, preferably α-olefins such as, for example, 1-butene or 1-hexene or ethylene in copolymerized form. Copolymers of propylene are preferably those copolymers in which at least 50% by weight of the copolymerized comonomers are propylene, more preferably at least 70% by weight.
Polypropylen im Sinne der vorliegenden Erfindung ist vorzugsweise isotaktisch.Polypropylene in the context of the present invention is preferably isotactic.
Bei Textilien im Sinne der vorliegenden Erfindung handelt es sich vorzugsweise um fadenförmige, d.h. lineare Gebilde, beispielsweise Fäden, Fasern, Filamente, Mikrofi- lamente, Mikrofasern, Monofilamente, Multifilamente, Stapelfasern, jeweils texturiert oder nicht texturiert.For the purposes of the present invention, textiles are preferably thread-like, i. linear structures, for example threads, fibers, filaments, microfilaments, microfibers, monofilaments, multifilaments, staple fibers, in each case textured or untextured.
Bei Textilien im Sinne der vorliegenden Erfindung kann es sich jedoch auch um Flächengebilde bzw. flächige Gebilde aus Polypropylen handeln, die vorzugsweise durch Kombination von mehreren fadenförmigen Gebilden aus Polypropylen erhältlich sind, beispielsweise Vliese (Non-wovens), Gewebe, Gestricke, Gewirke, Gelege und Gemenge, und die unter Verwendung von anderen ebenfalls fadenförmigen Gebilden hergestellt sein können, beispielsweise Synthesefasern wie z. B. Polyamid, Polyethy- len, Polyester oder Polyacryl, oder natürlichen Fasern wie beispielsweise Baumwolle. Bevorzugt handelt es sich jedoch um Flächengebilde bzw. flächige Gebilde oder Fasern oder Filamente, die entweder aus Polypropylen oder aus Mischungen von PoIy- ethylen und Polypropylen hergestellt sind.
In einer Ausführungsform der vorliegenden Erfindung ist zu behandelndes Textil aus Polypropylen vor der erfindungsgemäßen Behandlung nicht separat vorbehandelt, also weder hydrophiliert noch hydrophobiert.For the purposes of the present invention, textiles may, however, also be flat structures or planar structures made of polypropylene, which are preferably obtainable by combining a plurality of thread-like structures made of polypropylene, for example nonwovens, woven fabrics, knitted fabrics, knitted fabrics, scrims and mixtures, and which may be made using other also thread-like structures, such as synthetic fibers such. As polyamide, polyethylene len, polyester or acrylic, or natural fibers such as cotton. However, they are preferably sheet-like structures or fibers or filaments which are produced either from polypropylene or from mixtures of polyethylene and polypropylene. In one embodiment of the present invention, the textile of polypropylene to be treated is not pretreated separately before the treatment according to the invention, that is to say it is neither hydrophilized nor hydrophobized.
In einer Ausführungsform der vorliegenden Erfindung ist zu behandelndes Textil weder durch Plasmabehandlung noch durch beispielsweise Blitzentladungen vorbehandelt.In one embodiment of the present invention, textile to be treated is neither pretreated by plasma treatment nor by, for example, lightning discharges.
Erfindungsgemäß behandelt man Textil aus Propylen mit einer Emulgator-freien wäss- rigen Formulierung. Unter Behandeln wird dabei beispielsweise Tränken, Besprühen, kiss-roll-Auftrag und insbesondere Foulardieren verstanden. Erfindungsgemäß behandelt man mehrmals oder vorzugsweise nur einmal.According to the invention, textile is treated from propylene with an emulsifier-free aqueous formulation. Treating is understood as meaning, for example, soaking, spraying, kiss-roll application and, in particular, padding. According to the invention, it is treated several times or preferably only once.
Erfindungsgemäß behandelt man Textil aus Polypropylen mit Emulgator-freier wässri- ger Formulierung. Darunter ist im Rahmen der vorliegenden Erfindung zu verstehen, dass man wässriger Formulierung, mit der man Textil aus Polypropylen behandelt, keinen niedermolekularen Emulgator zusetzt, d.h. keine Emulgatoren mit Molekulargewichten bis zu 400 g/mol, in einer Ausführungsform keine Emulgatoren mit Molekulargewichten bis zu 500 g/mol. Im Falle von niedermolekularen Emulgatoren mit Molekulargewichtsverteilungen wird dabei jeweils Mn betrachtet.According to the invention, textile is treated from polypropylene with an emulsifier-free aqueous formulation. For the purposes of the present invention, this means that an aqueous formulation with which textile is treated from polypropylene does not add a low molecular weight emulsifier, ie no emulsifiers having molecular weights of up to 400 g / mol, in one embodiment no emulsifiers having molecular weights of up to 500 g / mol. In the case of low molecular weight emulsifiers with molecular weight distributions, in each case M n is considered.
Unter Emulgatoren sind im Rahmen der vorliegenden Erfindung oberflächenaktive anionische, kationische oder nicht-ionische Verbindungen zu verstehen, beispielsweise quaternäre Ammoniumsalze von Cs-C4o-Fettaminen, C8-C4o-Fettalkoholsulfate, C8-C4o-Fettalkoholphosphate, C8-C4o-Fettalkoholsulfonate, C8-C4o-Fettalkoholphos- phonate, Sulfonate von Cs-Cao-Alkylaromaten, mit im Bereich von 15 bis 150 Äquivalenten Alkylenoxid wie beispielsweise Ethylenoxid oder Propylenoxid alkoxylierter Cβ-CUo-Fettalkohol.For the purposes of the present invention, emulsifiers are surface-active anionic, cationic or nonionic compounds, for example quaternary ammonium salts of Cs-C4o fatty amines, C8-C4o-fatty alcohol sulfates, C8-C4o-fatty alcohol phosphates, C8-C4o-fatty alcohol sulfonates, C8- C4o-fatty alcohol phosphonates, sulfonates of Cs-Cao-alkylaromatics, with Cβ-CUo fatty alcohol alkoxylated in the range from 15 to 150 equivalents of alkylene oxide, for example ethylene oxide or propylene oxide.
In einer Ausführungsform der vorliegenden Erfindung wird unter „Emulgator-frei" ver- standen, dass insgesamt weniger als 0,1 Gew.-% vorstehend charakterisierter Emulgator in der im erfindungsgemäßen Verfahren eingesetzten wässrigen Formulierung sind, bevorzugt 0,001 bis 0,01 Gew.-%, bezogen auf die jeweilige wässrige Formulierung.In one embodiment of the present invention, "emulsifier-free" is understood as meaning that a total of less than 0.1% by weight of emulsifier characterized above is in the aqueous formulation used in the process according to the invention, preferably 0.001 to 0.01% by weight. %, based on the respective aqueous formulation.
Im erfindungsgemäßen Verfahren eingesetzte wässrige Formulierung enthält (a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe, im Rahmen der vorliegenden Erfindung auch als Silikonverbindung (a) bezeichnet, oderAqueous formulation used in the process according to the invention comprises (a) at least one silicone compound having at least one hydrophilic group, also referred to as silicone compound (a) in the context of the present invention, or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Dicarbon- säure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicar- bonsäure, im Rahmen der vorliegenden Erfindung auch als Ethylencopolymer (b) bezeichnet.
Silikonverbindung (a) kann beispielsweise eine quaternäre Ammoniumgruppe aufweisen.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or dicarboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid, also referred to in the context of the present invention as ethylene copolymer (b) , Silicone compound (a) may, for example, have a quaternary ammonium group.
Bei Silikonverbindungen (a) handelt es sich bevorzugt um solche Verbindungen, die aus mehreren Si(R1)(R2)-O-Einheiten aufgebaut sind, so dass sich Si-O- Ketten bilden, und die terminal entweder mit OH-Gruppen oder mit weiteren Resten R1 abgesättigt sind. Dabei können die Reste R1 und R2 verschieden oder mehrheitlich gleich sein und hauptsächlich gewählt aus C6-Ci4-Aryl, insbesondere Phenyl, oder Ci-C4-AIkVl, vorzugsweise unverzweigt, und insbesondere Methyl. Silikonverbindung (a) trägt mindes- tens eine hydrophile Gruppe, die sich beispielsweise an einem der terminalen oder - so vorhanden - einem der mittleren Si-Atome der oben beschriebenen Si-O-Ketten befinden kann. In einer Ausführungsform der vorliegenden Erfindung kann Silikonverbindung (a) zwei oder drei hydrophile Gruppen pro Molekül aufweisen, die verschieden oder vorzugsweise gleich sein können.Silicone compounds (a) are preferably those compounds which are made up of a plurality of Si (R 1 ) (R 2 ) -O units, so that Si-O chains are formed and terminally with either OH groups or are saturated with further radicals R 1 . The radicals R 1 and R 2 may be the same or a majority of the same and are mainly selected from C 6 -C 14 -aryl, in particular phenyl, or C 1 -C 4 -alkyl, preferably unbranched, and in particular methyl. Silicone compound (a) carries at least one hydrophilic group, which may be located, for example, on one of the terminal or, if present, one of the middle Si atoms of the Si-O chains described above. In one embodiment of the present invention, silicone compound (a) may have two or three hydrophilic groups per molecule, which may be different or preferably the same.
In einer Ausführungsform der vorliegenden Erfindung ist die hydrophile Gruppe bzw. sind die hydrophilen Gruppen über einen Spacer mit einem der terminalen oder - so vorhanden - einem der mittleren Si-Atome der oben beschriebenen Si-O-Ketten verbunden, beispielsweise einem C2-C2o-Alkylen-Spacer, der verzweigt oder vorzugsweise unverzweigt sein kann und in dem ein oder mehrere nicht-benachbarte CH2-Gruppen durch Sauerstoffatome ersetzt sein können.In one embodiment of the present invention, the hydrophilic group or groups are connected via a spacer to one of the terminal or, if present, one of the middle Si atoms of the above-described Si-O chains, for example a C 2 -C 2 oxide. Alkylene spacer, which may be branched or preferably unbranched and in which one or more non-adjacent CH 2 groups may be replaced by oxygen atoms.
In einer Ausführungsform der vorliegenden Erfindung weist Silikonverbindung (a) eine kinematische Viskosität im Bereich von 100 bis 100.000 m2/s auf, bestimmt bei 23°C.In one embodiment of the present invention, silicone compound (a) has a kinematic viscosity in the range of 100 to 100,000 m 2 / s, determined at 23 ° C.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Silikonverbindung (a) um eine Silikonverbindung, die mindestens eine NH-Gruppe oder mindestens eine C-OH-Gruppe oder mindestens eine Alkylenoxideinheit pro Molekül aufweist.In one embodiment of the present invention, silicone compound (a) is a silicone compound having at least one NH group or at least one C-OH group or at least one alkylene oxide unit per molecule.
Beispielsweise kann Silikonverbindung (a) mindestens eine NH-Gruppe aufweisen. Beispiele für NH-Gruppen sind NH(Ci-Cio-Alkyl)-Gruppen, insbesondere NH-Methyl, NH-Ethyl, NH(C6-Ci4-Aryl)-Gruppen, insbesondere NH(C6H5), NH(C7-C20-Aralkyl)- Gruppen, insbesondere NH-Benzyl, NH(C7-C2o-Alkylaryl)-Gruppen, insbesondere NH- (para-Tolyl), NH2-Gruppen, NH-CH2-CH2-NH2, -CONH2, NH-(CH2)3-NH2.For example, silicone compound (a) may have at least one NH group. Examples of NH groups are NH (C 1 -C 10 -alkyl) groups, in particular NH-methyl, NH-ethyl, NH (C 6 -C 4 -aryl) groups, in particular NH (C 6 H 5 ), NH ( C 7 -C 20 aralkyl) groups, in particular NH-benzyl, NH (C 7 -C 20 -alkylaryl) groups, in particular NH- (para-tolyl), NH 2 groups, NH-CH 2 -CH 2 -NH 2 , -CONH 2 , NH- (CH 2 ) 3 -NH 2 .
In einer Ausführungsform der vorliegenden Erfindung kann Silikonverbindung (a) mindestens eine C-OH-Gruppe aufweisen, die beispielsweise eine alkoholische OH-Gruppe sein kann oder eine COOH-Gruppe. Bevorzugt handelt es sich bei mindestens einer C-OH-Gruppe in Silikonverbindung (a) um eine sekundäre oder besonders bevorzugt um eine primäre C-OH-Gruppe, beispielsweise um eine CH2-OH-Gruppe, eine CH2-CH2-OH-Gruppe oder eine CH2-CH2-CH2-OH-Gruppe.
In einer Ausführungsform der vorliegenden Erfindung kann Silikonverbindung (a) mindestens eine Alkylenoxideinheit pro Molekül aufweisen, bevorzugt mindestens 3 bis 20 Alkylenoxideinheiten pro Molekül. Beispiele für Alkylenoxideinheiten sind C2-C6-Alky- lenoxideinheiten, beispielsweise Propylenoxideinheiten oder Butylenoxideinheiten oder bevorzugt Ethylenoxideinheiten.In one embodiment of the present invention, silicone compound (a) may have at least one C-OH group, which may be, for example, an alcoholic OH group or a COOH group. Preferably, at least one C-OH group in silicone compound (a) is a secondary or more preferably a primary C-OH group, for example a CH 2 -OH group, a CH 2 -CH 2 -OH Group or a CH 2 -CH 2 -CH 2 -OH group. In one embodiment of the present invention, silicone compound (a) may have at least one alkylene oxide unit per molecule, preferably at least 3 to 20 alkylene oxide units per molecule. Examples of alkylene oxide units are C 2 -C 6 -alkylene oxide units, for example propylene oxide units or butylene oxide units or preferably ethylene oxide units.
In einer speziellen Ausführungsform der vorliegenden Erfindung kann Silikonverbindung (a) mindestens eine Verbindung sein, die man durch Umsetzung von einem Überschuss an solchem Silikon, das mindestens eine Si-H-Gruppe pro Molekül, bevor- zugt mindestens zwei Si-H-Gruppen pro Molekül aufweist, in Gegenwart eines Katalysators auf Pt-Basis mit mindestens einer Verbindung der allgemeinen Formel I erhält,In a specific embodiment of the present invention, silicone compound (a) may be at least one compound obtained by reacting an excess of such silicone having at least one Si-H group per molecule, preferably at least two Si-H groups per Molecule, in the presence of a Pt-based catalyst with at least one compound of general formula I,
in denen die Variablen wie folgt definiert sind:where the variables are defined as follows:
R3 gewählt aus Ci-Cδ-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, , n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo- Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, bevorzugt Ci-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;R 3 is selected from C 1 -C 6 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert -butyl;
C2-C6-Alkenyl, beispielsweise Vinyl, 1 -AIIyI, 2-AIIyI, 3-AIIyI, Homoallyl, ω-Hexenyl, ω-Pentenyl und bevorzugt Vinyl oder 3-AIIyI,C 2 -C 6 alkenyl, for example vinyl, 1-allyl, 2-allyl, 3-allyl, homoallyl, ω-hexenyl, ω-pentenyl and preferably vinyl or 3-allyl,
R4 gleich oder verschieden und unabhängig voneinander gewählt aus Ethyl, Methyl und insbesondere Wasserstoff,R 4 is the same or different and is independently selected from ethyl, methyl and in particular hydrogen,
A1, A2 verschieden oder vorzugsweise gleich und gewählt aus NH, O,A 1 , A 2 different or preferably the same and selected from NH, O,
n eine ganze Zahl im Bereich von 1 bis 100, bevorzugt 2 bis 50.n is an integer in the range of 1 to 100, preferably 2 to 50.
Dabei bezieht sich Überschuss der Verbindung der allgemeinen Formel I auf die Äquivalente an Si-H-Gruppen in vorstehend genanntem Silikon.Excess of the compound of the general formula I refers to the equivalents of Si-H groups in the above-mentioned silicone.
Geeignete Katalysatoren auf Pt-Basis sind beispielsweise PtCI4, H2PtCl6-6 H2O, Platin- Olefin-Komplexe, auf feinverteiltem Kieselgel oder Aktivkohle oder auf Aluminiumoxid geträgertes Platin oder Komplexe von Pt mit Ethern, Aldehyden, Ketone, Alkoholaten, beispielsweise Norbornadien-Platindichlorid oder 1 ,5-Cyclooctadien-Platindichlorid.
In einer speziellen Ausführungsform der vorliegenden Erfindung setzt man solche Silikonverbindungen (a) ein, die durch Umsetzung der vorstehend genannten Silikonverbindung mit einem oder mehreren Diisocyanaten, vorzugsweise mit einem oder mehreren aliphatischen oder cycloaliphatischen Diisocyanaten erhältlich ist, beispielsweise 4,4'-Methylen-dicyclohexyldiisocyanat, Dodecamethylendiisocyanat, Tetramethylendii- socyanat und insbesondere Hexamethylendiisocyanat (HDI) und Isophorondiisocyanat. Andere geeignete Diisocyanate sind aromatische Diisocyanate wie 2,4-TDI, 2,6-TDI (Toluylendiisocyanat).Suitable Pt-based catalysts are, for example, PtCl 4 , H 2 PtCl 6 .6H 2 O, platinum-olefin complexes, finely divided silica gel or activated carbon or platinum supported on alumina or complexes of Pt with ethers, aldehydes, ketones, alcoholates, for example norbornadiene-platinum dichloride or 1,5-Cyclooctadiene platinum dichloride. In a specific embodiment of the present invention, use is made of those silicone compounds (a) obtainable by reacting the abovementioned silicone compound with one or more diisocyanates, preferably with one or more aliphatic or cycloaliphatic diisocyanates, for example 4,4'-methylene-dicyclohexyldiisocyanate , Dodecamethylene diisocyanate, tetramethylene diisocyanate and especially hexamethylene diisocyanate (HDI) and isophorone diisocyanate. Other suitable diisocyanates are aromatic diisocyanates such as 2,4-TDI, 2,6-TDI (tolylene diisocyanate).
In einer anderen speziellen Ausführungsform der vorliegenden Erfindung setzt man solche Silikonverbindungen (a) ein, die durch Umsetzung der vorstehend genannten Silikonverbindung mit einem oder mehreren alipahischen, aromatischen oder cycloaliphatischen Diisocyanaten und einem oder mehreren Diolen, Triolen, Diaminen, Tria- minen oder Polyaminen erhältlich ist, insbesondere aliphatischen Diolen, Triolen, Dia- minen, Triaminen oder Polyaminen wie beispielsweise Bis-(Dimethylaminopropyl)amin. Bevorzugte Diole sind Aminodiole wie beispielsweise N-Methyldiethanolamin, Dietha- nolamin, N-(n-Butyl)diethanolamin.In another specific embodiment of the present invention, use is made of those silicone compounds (a) obtainable by reacting the abovementioned silicone compound with one or more aliphatic, aromatic or cycloaliphatic diisocyanates and one or more diols, triols, diamines, triamines or polyamines is, in particular aliphatic diols, triols, diamines, triamines or polyamines such as bis (dimethylaminopropyl) amine. Preferred diols are amino diols such as N-methyldiethanolamine, diethanolamine, N- (n-butyl) diethanolamine.
Silikonverbindungen des vorstehend genannten Typs und ihre Herstellung sind bei- spielsweise in WO 05/121218 beschrieben.Silicone compounds of the aforementioned type and their preparation are described, for example, in WO 05/121218.
Im erfindungsgemäßen Verfahren eingesetzte wässrige Formulierung kann mindestens ein Ethylencopolymer (b) enthalten.An aqueous formulation used in the process according to the invention may contain at least one ethylene copolymer (b).
In einer Ausführungsform der vorliegenden Erfindung enthält Ethylencopolymer (b) einpolymerisiert:In one embodiment of the present invention, ethylene copolymer (b) contains in copolymerized form:
60 bis 95 Gew.-%, bevorzugt 65 bis 90 Gew.-% Ethylen und60 to 95 wt .-%, preferably 65 to 90 wt .-% of ethylene and
5 bis 40 Gew.-%, bevorzugt 10 bis 35 Gew.-% mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure, wobei Angaben in Gew.-% auf Ethylencopolymer (b) bezogen sind.5 to 40 wt .-%, preferably 10 to 35 wt .-% of at least one ethylenically unsaturated mono- or dicarboxylic acid or anhydride of an ethylenically unsaturated mono- or dicarboxylic acid, wherein in wt .-% are based on ethylene copolymer (b).
Bevorzugt handelt es sich bei mindestens einer ethylenisch ungesättigten Carbonsäure um eine Carbonsäure der allgemeinen Formel IlAt least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula II
Dabei sind in Formel Il die Reste wie folgt definiert:
R5 gewählt aus Wasserstoff,In formula II, the radicals are defined as follows: R 5 is selected from hydrogen,
Ci-Cio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; be- sonders bevorzugt Ci-C4-AIkVl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; especially preferred are C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
R6 gewählt aus Wasserstoff,R 6 is selected from hydrogen,
Ci-Cio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-
Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt CrC4-AIkVl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso- Butyl, sec.-Butyl und tert.-Butyl; COOH, COOCH3, COOC2H5.Amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; COOH, COOCH 3 , COOC 2 H 5 .
Ganz besonders bevorzugt ist R5 Methyl oder Wasserstoff und R6 Wasserstoff.Most preferably, R 5 is methyl or hydrogen and R 6 is hydrogen.
Als Anhydride von ethylenisch ungesättigten Carbonsäuren seien insbesondere Maleinsäureanhydrid und Itaconsäureanhydrid genannt.Particularly suitable anhydrides of ethylenically unsaturated carboxylic acids are maleic anhydride and itaconic anhydride.
Ethylencopolymer (b) kann ein oder mehrere weitere Comonomere einpolymerisiert enthalten, und zwar bis zu 40 Gew.-%, bevorzugt bis zu 35 Gew.-%, bezogen jeweils auf die Summe aus Ethylen und einpolymerisierter bzw. einpolymerisierten ethylenisch ungesättigten Carbonsäure(n). Beispielsweise kann einpolymerisiert sein: Vinylacetat, ein oder mehrere ethylenisch ungesättigte Carbonsäureester, bevorzugt der Formel IMEthylene copolymer (b) may contain one or more further comonomers in copolymerized form, specifically up to 40% by weight, preferably up to 35% by weight, based in each case on the sum of ethylene and copolymerized or copolymerized ethylenically unsaturated carboxylic acid (s). , For example, it may be copolymerized: vinyl acetate, one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula III
R7 gewählt aus Ci-Cio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt Ci-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,R 7 is selected from C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
R8 gewählt aus Wasserstoff,R 8 is selected from hydrogen,
Ci-Cio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso- Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; beson-
ders bevorzugt Ci-C4-AIkVl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso- Butyl, sec.-Butyl und tert.-Butyl,C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; special C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
R9 gewählt aus Wasserstoff, Ci-Cio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt CrC4-AIkVl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; COOH1 COOCH31 COOC2H5.R 9 selected from hydrogen, Ci-Cio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; COOH 1 COOCH 31 COOC 2 H 5 .
Ganz besonders bevorzugt ist R8 Wasserstoff oder Methyl und R9 Wasserstoff.Most preferably, R 8 is hydrogen or methyl and R 9 is hydrogen.
Ganz besonders bevorzugt ist R8 Wasserstoff oder Methyl und R9 Wasserstoff und R7 gewählt aus Methyl, Ethyl, n-Butyl und 2-Ethylhexyl.Most preferably, R 8 is hydrogen or methyl and R 9 is hydrogen and R 7 is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.
Ethylencopolymer (b) kann man vorteilhaft durch radikalisch initiierte Copolymerisation unter Hochdruckbedingungen herstellen, beispielsweise in gerührten Hochdruckautoklaven oder in Hochdruckrohrreaktoren. Die Herstellung in gerührten Hochdruckautoklaven ist bevorzugt. Gerührte Hochdruckautoklaven sind an sich bekannt, eine Beschreibung findet man in Ullmann's Encyclopedia of Industrial Che- mistry, 5. Auflage, Stichworte: Waxes, Bd. A 28, S. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. Bei ihnen verhält sich überwiegend das Verhältnis Länge/Durchmesser in Intervallen von 5:1 bis 30:1 , bevorzugt 10:1 bis 20:1. Die gleichfalls anwendbaren Hochdruckrohrreaktoren findet man ebenfalls in Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, Stichworte: Waxes, Bd. A 28, S. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.Ethylene copolymer (b) can be advantageously prepared by free-radically initiated copolymerization under high-pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred. High pressure autoclaves are known per se, a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. With them predominantly the ratio length / diameter at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1 behaves. The equally applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.
Geeignete Druckbedingungen für die Copolymerisation sind 500 bis 4000 bar, bevor- zugt 1500 bis 2500 bar. Die Reaktionstemperaturen liegen im Bereich von 170 bis 300°C, bevorzugt im Bereich von 200 bis 280°C.Suitable pressure conditions for the copolymerization are 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 200 to 280 ° C.
Die Copolymerisation kann man in Gegenwart eines Reglers durchführen. Als Regler verwendet man beispielsweise Wasserstoff oder einen aliphatischen Aldehyd oder ein aliphatisches Keton der allgemeinen Formel IMThe copolymerization can be carried out in the presence of a regulator. The regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula III
oder Mischungen derselben.
Dabei sind die Reste R8 gleich oder - insbesondere im Falle von Aldehyden - verschieden und ausgewählt aus Wasserstoff;or mixtures thereof. In this case, the radicals R 8 are identical or, in particular in the case of aldehydes, different and selected from hydrogen;
Ci-Cβ-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert- Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt Ci-C4-AIkVl wie Methyl, E- thyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert. -Butyl; C3-Ci2-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl.C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo Pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably Ci-C 4 -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl, sec-butyl and tert. butyl; C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
In einer besonderen Ausführungsform sind die Reste R8 miteinander unter Bildung eines 4- bis 13-gliedrigen Rings kovalent verbunden. So können beide Reste R8 beispielsweise gemeinsam sein: -(CHa)4-, -(CHb)S-, -(CH2)6, -(CH2)7-, -CH(CHa)-CH2-CH2-CH(CH3)- oder -CH(CHa)-CH2-CH2-CH2-CH(CH3)-.In a particular embodiment, the R 8 groups are covalently linked together to form a 4- to 13-membered ring. For example, both radicals R 8 may be common: - (CHa) 4 -, - (CHb) S-, - (CH 2 ) 6, - (CH 2 ) 7 -, -CH (CHa) -CH 2 -CH 2 -CH (CH 3 ) - or -CH (CHa) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
Als Starter für die radikalische Copolymerisation können die üblichen Radikalstarter wie beispielsweise organische Peroxide, Sauerstoff oder Azoverbindungen eingesetzt werden. Auch Mischungen mehrerer Radikalstarter sind geeignet.As initiators for the radical copolymerization, the usual radical initiators such as organic peroxides, oxygen or azo compounds can be used. Also mixtures of several radical starters are suitable.
Geeignete Peroxide, ausgewählt aus den kommerziell erhältlichen Substanzen, sind Didekanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert.-Amylper- oxy-2-ethylhexanoat, Dibenzoylperoxid, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butyl- peroxydiethylacetat, tert.-Butylperoxydiethylisobutyrat, 1 ,4-Di(tert.-butylperoxycar- bonyl)-cyclohexan als Isomerengemisch, tert.-Butylperisononanoat 1 ,1-Di-(tert.-butyl- peroxy)-3,3,5-trimethylcyclohexan, 1 ,1-Di-(tert.-butylperoxy)-cyclohexan, Methyl- isobutylketonperoxid, tert.-Butylperoxyisopropylcarbonat, 2,2-Di-tert.-butylperox)butan oder tert.-Butylperoxacetat;Suitable peroxides selected from the commercially available substances are didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2 ethyl hexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxydiethyl isobutyrate, 1,4-di (tert-butyl peroxycarbonyl) cyclohexane as isomer mixture, tert-butyl perisononanoate 1, 1-di- (tert-butyl-peroxy ) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert. Butylperoxacetat;
tert.-Butylperoxybenzoat, Di-tert.-amylperoxid, Dicumylperoxid, die isomeren Di-(tert- butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert.-butylperoxyhexan, tert.-Butyl- cumylperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hex-3-in, Di-tert.-butylperoxid, 1 ,3-Diisopropylbenzolmonohydroperoxid, Cumolhydroperoxid oder tert.-Butylhydro- peroxid; oder dimere oder trimere Ketonperoxide, wie sie aus EP-A 0 813 550 bekannt sind.tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, tert-butyl cumyl peroxide, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or dimeric or trimeric ketone peroxides, as are known from EP-A 0 813 550.
Als Peroxide sind Di-tert.-butylperoxid, tert.-Butylperoxypivalat, tert.-Butylperoxyiso- nonanoat oder Dibenzoylperoxid oder Gemische derselben besonders geeignet. Als Azoverbindung sei Azobisisobutyronitril („AIBN") beispielhaft genannt. Radikalstarter werden in für Polymerisationen üblichen Mengen dosiert.
Zahlreiche kommerziell erhältliche organische Peroxide werden mit sogenannten Phlegmatisierern versetzt, bevor sie verkauft werden, um sie besser handhabbar zu machen. Als Phlegmatisierer sind beispielsweise Weißöl oder Kohlenwasserstoffe wie insbesondere Isododekan geeignet.As peroxides, di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisone nonanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. As an azo compound, azobisisobutyronitrile ("AIBN") is mentioned as an example Radical starters are metered in amounts customary for polymerizations. Many commercially available organic peroxides are added to so-called phlegmatizers before they are sold to make them more manageable. For example, white oil or hydrocarbons, in particular isododecane, are suitable as phlegmatizers.
In einer Ausführungsform der vorliegenden Erfindung weisen Ethylencopolymere (b) eine Schmelzemassefließrate (MFR) im Bereich von 1 bis 500 g/10 min, bevorzugt 5 bis 200 g/10 min, besonders bevorzugt 7 bis 50 g/10 min auf, gemessen bei 160°C und einer Belastung von 325 g nach DIN 53735.In one embodiment of the present invention, ethylene copolymers (b) have a melt flow rate (MFR) in the range of 1 to 500 g / 10 min, preferably 5 to 200 g / 10 min, more preferably 7 to 50 g / 10 min, measured at 160 ° C and a load of 325 g according to DIN 53735.
In einer Ausführungsform der vorliegenden Erfindung weisen Ethylencopolymere (b) eine kinematische Schmelzeviskosität v im Bereich von 500 bis 10.000 mm2/s, bevorzugt im Bereich von 800 bis 4.000 mm2/s auf, gemessen nach DIN 51562.In one embodiment of the present invention, ethylene copolymers (b) have a kinematic melt viscosity v in the range of 500 to 10,000 mm 2 / s, preferably in the range of 800 to 4,000 mm 2 / s, measured according to DIN 51562.
In einer Ausführungsform der vorliegenden Erfindung liegen die Schmelzbereiche von Ethylencopolymeren (b) im Bereich von 60 bis 1 15°C, bevorzugt im Bereich von 65 bis 1 100C, bestimmt durch DSC nach DIN 51007.In one embodiment of the present invention, the melting ranges of ethylene copolymers (b) in the range of 60 to 1 15 ° C, preferably in the range of 65 to 1 10 0 C, determined by DSC according to DIN 51007.
In einer Ausführungsform der vorliegenden Erfindung beträgt die Dichte von Ethylen- copolymer (b) 0,89 bis 1 ,10 g/cm3, bevorzugt 0,92 bis 0,94 g/cm3, bestimmt nach DIN 53479.In one embodiment of the present invention, the density of ethylene copolymer (b) is from 0.89 to 1.10 g / cm 3 , preferably from 0.92 to 0.94 g / cm 3 , determined according to DIN 53479.
Ethylencopolymer (b) kann ein alternierendes Copolymer sein oder ein Blockcopolymer oder vorzugsweise ein statistisches Copolymer.Ethylene copolymer (b) may be an alternating copolymer or a block copolymer or preferably a random copolymer.
Ethylencopolymer (b) kann bezüglich einpolymerisierter ethylenisch ungesättigter Carbonsäure und/oder ethylenisch ungesättigter C4-Cio-Dicarbonsäure als freie Säure vorliegen oder partiell oder vollständig neutralisiert sein, beispielsweise mit Alkalimetall wie z. B. Natrium oder Kalium oder mit Erdalkalimetall wie beispielsweise Magnesium oder Calcium oder mit Ammoniak oder organischem Amin, insbesondere Ci-C4-Mono- alkylamin, Di-Ci-C4-alkylamin, Tri-Ci-C4-alkylamin oder Tetra-Ci-C4-alkylammonium neutralisiert sein. Auch kann gegebenenfalls einpolymerisisiertes Anhydrid von ethylenisch ungesättigter C4-Cio-Dicarbonsäure in hydrolysierter Form vorliegen.Ethylene copolymer (b) can be present as free acid with respect to copolymerized ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated C 4 -C 10 -dicarboxylic acid or be partially or completely neutralized, for example with alkali metal such as. As sodium or potassium or with alkaline earth metal such as magnesium or calcium or with ammonia or organic amine, in particular C 1 -C 4 monoalkylamine, di-C 1 -C 4 -alkylamine, tri-C 1 -C 4 -alkylamine or tetra-C 1 -C 4 be neutralized alkylammonium. If desired, copolymerized anhydride of ethylenically unsaturated C 4 -C 10 -dicarboxylic acid may also be present in hydrolyzed form.
In einer Ausführungsform der vorliegenden Erfindung sind bis zu 90 mol-%, bevorzugt bis zu 75 ιmol-% der Carbonsäuregruppen von Ethylencopolymer (b) mit Hydroxyalky- lammonium insbesondere der Formel (Ci-C4-Alkyl)x(C2-C4-ω-Hydroxyalkyl)yNH4-x-y neutralisiert, wobeiIn one embodiment of the present invention, up to 90 mol%, preferably up to 75, mol% of the carboxylic acid groups of ethylene copolymer (b) with hydroxyalkylammonium, in particular of the formula (C 1 -C 4 -alkyl) x (C 2 -C 4 -ω- Hydroxyalkyl) y NH4-x- y neutralized, wherein
x eine ganze Zahl im Bereich von null bis drei, bevorzugt null oder eins, y eine ganze Zahl im Bereich von eins bis vier ist mit der Maßgabe, dass die Summe aus x und y den Wert vier nicht überschreitet.
Bevorzugte Beispiele für Ci-C4-ω-Hydroxyalkyl sind 3-Hydroxypropyl, 4-Hydroxybutyl und insbesondere 2-Hydroxyethyl, im Folgenden auch als Hydroxyethyl bezeichnet.x is an integer in the range of zero to three, preferably zero or one, y is an integer in the range of one to four, with the proviso that the sum of x and y does not exceed four. Preferred examples of C 1 -C 4 -ω-hydroxyalkyl are 3-hydroxypropyl, 4-hydroxybutyl and in particular 2-hydroxyethyl, also referred to below as hydroxyethyl.
Besonders bevorzugte Beispiele für Hydroxyalkylammonium sind N,N-Dihydroxyethyl- ammonium, N-Methyl-N-Hydroxyethylammonium, N,N-Dimethyl-N-hydroxyethyl- ammonium, N-Methyl-N,N-dihydroxyethylammonium, N-n-Butyl-hydroxyethyl- ammonium, N-n-Butyl-N,N-dihydroxyethylammonium.Particularly preferred examples of hydroxyalkylammonium are N, N-dihydroxyethylammonium, N-methyl-N-hydroxyethylammonium, N, N-dimethyl-N-hydroxyethylammonium, N-methyl-N, N-dihydroxyethylammonium, Nn-butyl-hydroxyethylammonium ammonium, Nn-butyl-N, N-dihydroxyethylammonium.
Weitere geeignete organische Amine zum Neutralisieren sind beispielsweise Morpho- Nn, Imidazol, N4-Amine, Imidazoline, Oxazoline, Triazole und Fettsäurealkanolamine.Further suitable organic amines for neutralizing are, for example, morphine-Nn, imidazole, N4-amines, imidazolines, oxazolines, triazoles and fatty acid alkanolamines.
Geeignete Mittel zum Neutralisieren sind weiterhin KOH, NaOH, Ca(OH)2, NaHCO3, Na2CO3, K2CO3 und KHCO3.Suitable neutralizing agents are furthermore KOH, NaOH, Ca (OH) 2, NaHCO 3, Na 2 CO 3 , K 2 CO 3 and KHCO 3 .
Im erfindungsgemäßen Verfahren eingesetzte wässrige Formulierungen weisen für den Fall, dass sie Ethylencopolymer (b) enthalten, vorzugsweise einen basischen pH-Wert auf, beispielsweise pH-Werte von 7,5 bis 14, bevorzugt von 8 oder höher und besonders bevorzugt von 8,5 oder höher.In the case where they contain ethylene copolymer (b), aqueous formulations used in the process according to the invention preferably have a basic pH, for example pH values from 7.5 to 14, preferably from 8 or higher and particularly preferably from 8.5 or higher.
In einer Ausführungsform der vorliegenden Erfindung kann man Textil aus Polypropylen bei einer Temperatur im Bereich von 0°C bis 145°C, bevorzugt bis 130°C behandeln. Wenn man bei Temperaturen im Bereich von 100 bis 145°C zu behandeln wünscht, so muss man bei einem Druck behandeln, der über Normaldruck liegt. Wünscht man bei Temperaturen im Bereich von 0 bis 100°C zu arbeiten, so ist auch Normaldruck geeignet.In one embodiment of the present invention, polypropylene fabric may be treated at a temperature in the range of 0 ° C to 145 ° C, preferably up to 130 ° C. If you want to treat at temperatures in the range of 100 to 145 ° C, so you have to treat at a pressure that is above normal pressure. If you want to work at temperatures in the range of 0 to 100 ° C, then normal pressure is suitable.
In einer Ausführungsform der vorliegenden Erfindung behandelt man Textil aus Polypropylen mit einer wässrigen Formulierung, die auch als wässrige Flotte bezeichnet werden kann. Wünscht man das erfindungsgemäße Verfahren so durchzuführen, dass man zu behandelndes Textil aus Polypropylen mit einer wässrigen Flotte behandelt, so kann man die Flottenaufnahme so wählen, dass durch das erfindungsgemäße Verfahren eine Flottenaufnahme von 25 Gew.-% bis 95 Gew.-%, bevorzugt 60 bis 90 Gew.-% resultiert.In one embodiment of the present invention, polypropylene fabric is treated with an aqueous formulation, which may also be referred to as an aqueous liquor. If it is desired to carry out the process according to the invention in such a way that the polypropylene textile to be treated is treated with an aqueous liquor, the liquor pickup can be selected such that a liquor uptake of 25% by weight to 95% by weight is preferred by the process according to the invention 60 to 90 wt .-% results.
In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren in gängigen Maschinen durch, die für die Ausrüstung von Textilien eingesetzt werden, beispielsweise Foulards. Bevorzugt sind Foulards mit senkrechtem Texti- linzug, die als wesentliches Element zwei aufeinandergepresste Rollen enthalten, durch die das Textil aus Polypropylen geführt wird. Oberhalb der Rollen ist vorzugs- weise wässrige Formulierung eingefüllt und benetzt das Textil aus Polypropylen. Durch den Druck wird das Textil aus Polypropylen abgequetscht und ein konstanter Auftrag gewährleistet. Bei anderen bevorzugten Foulards wird Textil aus Polypropylen zu-
nächst durch ein Tauchbad geführt und anschließend nach oben durch zwei aufeinan- dergepresste Rollen. In letzterem Falle spricht man auch von Foulards mit senkrechtem Textileinzug von unten. Foulards sind beispielsweise beschrieben in Hans-Karl Rouette, „Handbuch der Textilveredlung", Deutscher Fachverlag 2003, S. 618 bis 620.In one embodiment of the present invention, the method according to the invention is carried out in conventional machines used for finishing textiles, for example foulards. Preference is given to foulards with vertical textile draw, which contain as an essential element two rollers pressed against one another, through which the textile is guided out of polypropylene. Above the rollers, aqueous formulation is preferably filled in and wets the textile made of polypropylene. The pressure squeezes off the textile made of polypropylene and ensures a constant application. In other preferred foulards, textile is made of polypropylene. pass through an immersion bath and then upwards through two rollers pressed onto each other. In the latter case one speaks also of foulards with vertical Textileinzug from below. Foulards are described, for example, in Hans-Karl Rouette, "Handbuch der Textilveredlung", Deutscher Fachverlag 2003, p. 618-620.
In einer Ausführungsform der vorliegenden Erfindung kann man das erfindungsgemäße Verfahren nach Art eines Ausziehverfahrens durchführen, beispielsweise durch Sprühen, Pflatschen, Kiss-roll oder durch Ausdrucken.In one embodiment of the present invention, the process according to the invention can be carried out in the manner of an exhaust process, for example by spraying, patting, kiss-rolling or by printing.
In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren nach Art eines Ausziehverfahrens durch, und zwar mit einer Flottenaufnahme im Bereich von 1 bis 50%, bevorzugt 20 bis 40%.In one embodiment of the present invention, the process according to the invention is carried out in the manner of an exhaust process, with a liquor pick-up in the range from 1 to 50%, preferably from 20 to 40%.
In einer Ausführungsform der vorliegenden Erfindung kann man im Anschluss an die Behandlung von Textil aus Polypropylen thermisch behandeln, beispielsweise durch Trocknen bei Temperaturen im Bereich von 30 bis 100°C oder durch thermisches Fixieren bei Temperaturen im Bereich von mindestens 100, bevorzugt mindestens 101 °C bis zu 150°C, bevorzugt bis zu 135°C.In one embodiment of the present invention, following the treatment of textile, polypropylene may be thermally treated, for example by drying at temperatures in the range of 30 to 100 ° C or by thermal fixing at temperatures in the range of at least 100, preferably at least 101 ° C. up to 150 ° C, preferably up to 135 ° C.
In einer Ausführungsform der vorliegenden Erfindung kann man über einen Zeitraum von 10 Sekunden bis zu 30 Minuten thermisch behandeln, bevorzugt 30 Sekunden bis 10 Minuten.In one embodiment of the present invention, it is possible to heat treat up to 30 minutes over a period of 10 seconds, preferably 30 seconds to 10 minutes.
In einer Ausführungsform der vorliegenden Erfindung führt man zwei thermische Be- handlungsschritte bei verschiedenen Temperaturen durch, beispielsweise trocknet man in einem ersten Schritt bei Temperaturen im Bereich von 30 bis 100°C über einen Zeitraum von 10 Sekunden bis 20 Minuten, und danach fixiert man bei Temperaturen im Bereich von 101 bis 135°C über einen Zeitraum von 30 Sekunden bis zu 3 Minuten.In one embodiment of the present invention, two thermal treatment steps are carried out at different temperatures, for example drying in a first step at temperatures in the range of 30 to 100 ° C over a period of 10 seconds to 20 minutes, and then fixed at Temperatures in the range of 101 to 135 ° C over a period of 30 seconds to 3 minutes.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung kann im erfindungsgemäßen Verfahren eingesetzte wässrige Formulierung mindestens eine Silikonverbindung (a) und mindestes eine Ethylencopolymer (b) enthalten.In a preferred embodiment of the present invention, the aqueous formulation used in the process according to the invention may contain at least one silicone compound (a) and at least one ethylene copolymer (b).
In einer Ausführungsform der vorliegenden Erfindung kann im erfindungsgemäßen Verfahren eingesetzte wässrige Formulierung einen oder mehrere Zusätze (d) enthalten. Geeignete Zusätze (d) sind beispielsweise organische Lösungsmittel, organische Lösungsmittel wie Dimethylsulfoxid (DMSO), N-Methylpyrrolidon (NMP), N-Ethylpyrro- lidon (NEP), Ethylenglykol, Diethylenglykol, Butylykol, Dibutylglykol, und beispielsweise Restalkohol-freies alkoxyliertes n-C4-C6-Alkanol, bevorzugt Restalkohol-freies ein- bis 10-fach, besonders bevorzugt 3- bis 6-fach ethoxyliertes n-C4-C6-Alkanol. Dabei ist unter Restalkohol das jeweils nicht alkoxylierte n-C4-C6-Alkanol zu verstehen.
Ein weiterer Gegenstand der vorliegenden Erfindung sind wässrige Formulierungen, enthaltendIn one embodiment of the present invention, aqueous formulation used in the process according to the invention may contain one or more additives (d). Suitable additives (d) are, for example, organic solvents, organic solvents such as dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethylene glycol, diethylene glycol, butyl glycol, dibutyl glycol, and, for example, residual alcohol-free alkoxylated n- C4-C6-alkanol, preferably residual alcohol-free one to 10-fold, particularly preferably 3- to 6-fold ethoxylated n-C4-C6-alkanol. In this case, residual alcohol is to be understood as meaning the respectively non-alkoxylated n-C4-C6-alkanol. Another object of the present invention are aqueous formulations containing
(a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe oder(a) at least one silicone compound having at least one hydrophilic group or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or dicarboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid.
Silikonverbindung (a) und Ethylencopolymer (b) sind vorstehend beschrieben.Silicone compound (a) and ethylene copolymer (b) are described above.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße wässrige Formulierung:In one embodiment of the present invention, aqueous formulation according to the invention comprises:
0,1 bis 20 Gew.-%, bevorzugt 0,5 bis 10 Gew.-% Silikonverbindung (a) oder 1 bis 25 Gew.-%, bevorzugt 2 bis 25 Gew.-% Ethylencopolymer (b).0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-% silicone compound (a) or 1 to 25 wt .-%, preferably 2 to 25 wt .-% ethylene copolymer (b).
Erfindungsgemäße wässrige Formulierung enthält in einer Ausführungsform der vorliegenden Erfindung keine Farbmittel wie beispielsweise Pigmente, Farbstoffe oder Dispersionsfarbstoffe.In one embodiment of the present invention, the aqueous formulation according to the invention contains no colorants such as, for example, pigments, dyes or disperse dyes.
Erfindungsgemäße wässrige Formulierung kann null bis insgesamt 5 Gew.-% Zusätze enthalten, bevorzugt 0,5 bis 3,5 Gew.-%, bezogen auf gesamte erfindungsgemäße wässrige Formulierung.Aqueous formulation according to the invention may contain from zero to a total of 5% by weight of additives, preferably from 0.5 to 3.5% by weight, based on the total aqueous formulation according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Textilien aus Polypropylen, behandelt nach dem erfindungsgemäßen Verfahren. Erfindungsgemäße Textilien zeigen eine gute und im Allgemeinen dauerhafte Hydrophilie, die sich beispielsweise durch die Bestimmung der Einsinktiefe eines Wassertropfens nachweisen lassen kann. Weiterhin beobachtet man bei solchen erfindungsgemäßen Textilien aus Polypropylen, die man als oder zur Herstellung von Bekleidung verwendet, einen verbesserten Tra- gekomfort.Another object of the present invention are textiles made of polypropylene, treated by the method according to the invention. Textiles of the invention show a good and generally durable hydrophilicity, which can be detected, for example, by determining the sinking depth of a drop of water. Furthermore, in the case of such textiles of polypropylene according to the invention, which are used as or for the production of clothing, an improved trac comfort is observed.
In einer Ausführungsform der vorliegenden Erfindung umfassen erfindungsgemäße Textilien aus Polypropylen 0,1 Gew.-%0 bis 5 Gew.-%, bevorzugt 0,5 Gew.-%0 bis 3 Gew.-% Silikonverbindung (a) oder 0,1 Gew.-%o bis 5 Gew.-%, bevorzugt 0,5 Gew.-%o bis 3 Gew.-% Ethylencopolymer (b).In one embodiment of the present invention, polypropylene textiles according to the invention comprise 0.1% by weight 0 to 5% by weight, preferably 0.5% by weight 0 to 3% by weight of silicone compound (a) or 0.1% by weight % to 5% by weight, preferably 0.5% to 0% to 3% by weight of ethylene copolymer (b).
Erfindungsgemäße Textilien aus Polypropylen lassen sich beispielsweise vorteilhaft als Hygienevliese, als Brandschutzmittel für Baumaterialien wie beispielsweise Mörtel oder Beton, als Bestandteil von Sportbekleidung, Unterwäsche, Sicherheitsbekleidung oder Filtern einsetzen.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Baumaterialien wie beispielsweise Mörtel oder insbesondere Beton, enthaltend mindestens ein erfindungsgemäßes Textil aus Polypropylen, vorzugsweise in Form von Mikrofasern oder Mikrofi- lamenten. In erfindungsgemäßen Baumaterialien sind erfindungsgemäße Textilien ausgezeichnet verteilt, und die Anbindung ist gut. Außerdem neigen erfindungsgemäße Baumaterialien, in Bauwerken wie beispielsweise Gebäuden verbaut, bei hohen Temperaturen nicht so stark zum Platzen. Zur Herstellung von Baumaterialien, die mindestens ein erfindungsgemäßes Textil enthalten, kann man beispielsweise so vorgehen, dass man erfindungsgemäßes Textil in konventionelles Baumaterial wie beispielsweise Beton oder Mörtel einbringt und untermischt. Zur Verarbeitung kann man dann erfindungsgemäßes Baumaterial wie beispielsweise erfindungsgemäßen Beton nach an sich bekannten Methoden gießen, oder man kann erfindungsgemäßes Baumaterial, insbesondere erfindungsgemäßen Mörtel nach an sich bekannten Methoden aufbringen.Polypropylene textiles according to the invention can be used, for example, advantageously as hygiene fleeces, as fire-retardants for building materials such as, for example, mortar or concrete, as a constituent of sportswear, underwear, safety clothing or filters. Another object of the present invention are building materials such as mortar or concrete in particular containing at least one inventive textile made of polypropylene, preferably in the form of microfibers or microfilaments. In building materials according to the invention textiles according to the invention are excellently distributed, and the connection is good. In addition, building materials according to the invention, built into structures such as buildings, tend not to burst so much at high temperatures. For the production of building materials containing at least one textile according to the invention, it is possible to proceed, for example, by introducing and mixing in textile according to the invention in conventional building material such as, for example, concrete or mortar. For processing, it is then possible to cast building material according to the invention, such as concrete according to the invention, according to methods known per se, or to apply building material according to the invention, in particular mortar according to the invention, by methods known per se.
Weitere Gegenstände der vorliegenden Erfindung sind Hygienevliese, Bekleidungstextilien wie Sportbekleidung, Unterwäsche oder Sicherheitsbekleidung sowie Geotexti- lien, hergestellt aus oder unter Verwendung von erfindungsgemäßem Textil.Further objects of the present invention are hygiene mats, clothing textiles such as sportswear, underwear or safety clothing and geotextiles, made of or using textile according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Hygienevliese, beispielsweise für Windeln oder Damenbinden, hergestellt unter Verwendung von erfindungsgemäßem Textil.A further subject of the present invention are hygiene mats, for example for diapers or sanitary napkins, produced using textile according to the invention.
Die Erfindung wird durch Beispiele illustriert.The invention is illustrated by examples.
Allgemeine Bemerkungen:General remarks:
Es wurden stets folgende Geräte verwendet:The following devices were always used:
Foulard: Hersteller Fa. Mathis, Typ Nr. HVF12085, Anpressdruck 1 - 3 bar. Der An- pressdruck wurde stets so eingestellt, dass die Flottenaufnahme (bezogen auf das Warengewicht) 70 bis 100% betrug. Die Flotte hatte Zimmertemperatur, wenn nicht anders angegeben. Trockner/Fixiergerät: kontinuierlich arbeitender Trockner der Fa. Mathis THN 12589
Die Einsinkzeit wurde nach dem TEGEWA-T ropfentest bestimmt.Foulard: Manufacturer Fa. Mathis, type no. HVF12085, contact pressure 1 - 3 bar. The contact pressure was always set so that the liquor pick-up (based on the weight of the goods) was 70 to 100%. The fleet had room temperature, unless stated otherwise. Dryer / Fixer: continuous dryer of the company Mathis THN 12589 The sinking time was determined by the TEGEWA ear test.
I. Herstellung von Silikonverbindungen 1.1 Herstellung einer hydrophilen Silikonverbindung (a.1 )I. Preparation of Silicone Compounds 1.1 Preparation of a Hydrophilic Silicone Compound (a.1)
480 g eines α,ω-Dihydrogenpolydimethylsiloxans mit 0,055 Gew.-% Si-gebundenem Wasserstoff und einem Wassergehalt von 50 Gew.-ppm wurden mit 268 g eines PoIy- ethers der Formel 1.1480 g of an α, ω-Dihydrogenpolydimethylsiloxans with 0.055 wt .-% Si-bonded hydrogen and a water content of 50 ppm by weight were mixed with 268 g of a polyether of formula 1.1
n = 1° mit einem Wassergehalt von 686 Gew.-ppm gemischt und auf 100 °C erwärmt. Danach wurden 0,14 g einer (bezogen auf elementares Platin) 2,7 Gew.-% Lösung eines Pt- 1 ,3-Divinyl-1 ,1 ,3,3-tetramethyldisiloxan-Komplexes in α,ω-Divinylpolydimethylsiloxan mit einer dynamischen Viskosität von 1000 mPa-s zugesetzt, bestimmt bei 25°C. Die Temperatur stieg um etwa 19°C an, und es entstand ein klares Produkt. Man rührte eine Stunde bei 100 bis 1 10°C, danach war der Umsatz des Si-gebundenen Wasserstoffs vollständig. n = 1 ° mixed with a water content of 686 ppm by weight and heated to 100 ° C. Thereafter, 0.14 g of a (based on elemental platinum) 2.7 wt .-% solution of a Pt-1, 3-divinyl-1,1,3,3-tetramethyldisiloxan complex in α, ω-Divinylpolydimethylsiloxan with a dynamic Viscosity of 1000 mPa-s added, determined at 25 ° C. The temperature rose by about 19 ° C, and there was a clear product. The mixture was stirred for one hour at 100 to 1 10 ° C, then the conversion of Si-bonded hydrogen was complete.
Danach gab man 49,5 g Bis-(dimethylaminopropyl)amin und 65 g Hexamethylendiiso- cyanat nacheinander zu sowie 50 mg Di-n-butylzinndilaurat. Man rührte 2 Stunden bei 100°C und kühlte auf 70°C ab. Man gab 35 g Essigsäure und 225 g Diethylenmomo-n- butylether zu. Man erhielt (a.1 ) als transparentes braunes Öl mit einer kinematischen Viskosität von 4.900 mm2/s, bestimmt bei 25°C, und einer Aminzahl von 0,47. Dabei entspricht die Aminzahl der Anzahl ml einer 1 N HCl, die zur Neutralisation von 1 g (a.1) erforderlich sind.Thereafter, 49.5 g of bis (dimethylaminopropyl) amine and 65 g of hexamethylene diisocyanate were added in succession and 50 mg of di-n-butyltin dilaurate. The mixture was stirred for 2 hours at 100 ° C and cooled to 70 ° C from. 35 g of acetic acid and 225 g of diethylene momo-n-butyl ether were added. (A.1) was obtained as a transparent brown oil with a kinematic viscosity of 4,900 mm 2 / s, determined at 25 ° C., and an amine number of 0.47. The amine number corresponds to the number of ml of 1 N HCl required to neutralize 1 g (a.1).
Rührte man in 40 g der vorstehend beschriebenen Lösung 60 g Wasser ein, so erhielt man eine Emulsion mit einer Aminzahl von 0,19.
When 60 g of water were stirred into 40 g of the solution described above, an emulsion having an amine number of 0.19 was obtained.
Herstellung einer Silikonverbindung (a.2)Preparation of a silicone compound (a.2)
245 g eines α,ω-Dihydrogenpolydimethylsiloxans mit 0,055 Gew.-% Si-gebundenem Wasserstoff und einem Wassergehalt von 50 Gew.-ppm wurden mit 500 g eines PoIy- ethers der Formel 1.2245 g of an α, ω-Dihydrogenpolydimethylsiloxans with 0.055 wt .-% Si-bonded hydrogen and a water content of 50 ppm by weight were mixed with 500 g of a polyether of formula 1.2
mit einer Jodzahl von 13,7 g b/I OO g 1.2 und einem Wassergehalt von 978 Gew.-ppm gemischt und auf 100 °C erwärmt. Danach wurden 0,14 g einer (bezogen auf elemen- tares Platin) 2,7 Gew.-% Lösung eines Pt-1 ,3-Divinyl-1 ,1 ,3,3-tetramethyldisiloxan- Komplexes (als Katalysator) in α,ω-Divinylpolydimethylsiloxan mit einer dynamischen Viskosität von 1000 mPa-s zugesetzt, bestimmt bei 25°C. Die Temperatur stieg um etwa 6°C an, woraufhin die gleiche Menge Katalysator nachdosiert wurde, und es entstand ein klares Produkt. Man rührte eine Stunde bei 100 bis 1 10°C, danach war der Umsatz des Si-gebundenen Wasserstoffs vollständig. Man erhielt ein Zwischenprodukt.mixed with an iodine value of 13.7 g b / I OO g 1.2 and a water content of 978 ppm by weight and heated to 100 ° C. Thereafter, 0.14 g of a (based on elemental platinum) 2.7 wt .-% solution of a Pt-1, 3-divinyl-1,1,3,3-tetramethyldisiloxane complex (as a catalyst) in α, ω-Divinylpolydimethylsiloxan added with a dynamic viscosity of 1000 mPa-s, determined at 25 ° C. The temperature rose by about 6 ° C, after which the same amount of catalyst was replenished, and there was a clear product. The mixture was stirred for one hour at 100 to 1 10 ° C, then the conversion of Si-bonded hydrogen was complete. An intermediate product was obtained.
735 g des vorstehend beschriebenen Zwischenprodukts wurden vorgelegt und 25,5 g Bis-(dimethylaminopropyl)amin und 33,5 g Hexamethylendiisocyanat nacheinander zugesetzt sowie 50 mg Di-n-butylzinndilaurat. Man rührte 2 Stunden bei 100°C und kühlte auf 70°C ab. Man gab 17,5 g Essigsäure und 205 g Diethylenmomo-n-butylether zu. Man erhielt (a.2) als transparentes braunes Öl mit einer kinematischen Viskosität von 7.800 mm2/s, bestimmt bei 25°C, und einer Aminzahl von 0,26.735 g of the above-described intermediate were initially charged and 25.5 g of bis (dimethylaminopropyl) amine and 33.5 g of hexamethylene diisocyanate were added in succession and 50 mg of di-n-butyltin dilaurate. The mixture was stirred for 2 hours at 100 ° C and cooled to 70 ° C from. 17.5 g of acetic acid and 205 g of diethylene momo-n-butyl ether were added. (A.2) was obtained as a transparent brown oil with a kinematic viscosity of 7,800 mm 2 / s, determined at 25 ° C., and an amine number of 0.26.
Rührte man in 40 g der vorstehend beschriebenen Lösung 60 g Wasser ein, so erhielt man eine wässrige Emulsion von (a.2) mit einer Aminzahl von 0,1.When 60 g of water were stirred into 40 g of the solution described above, an aqueous emulsion of (a.2) having an amine number of 0.1 was obtained.
II. Herstellung von erfindungsgemäßen Textilien aus PolypropylenII. Production of Polypropylene Textiles According to the Invention
11.1 Herstellung von erfindungsgemäßem Textil T111.1 Production of Textile T1 According to the Invention
Ein Gewebe (100% Polypropylen, 150 g/m2 Flächengewicht) wurde mit einer wässrigen Formulierung foulardiert, bestehend ausA fabric (100% polypropylene, 150 g / m 2 basis weight) was padded with an aqueous formulation consisting of
30 g/l wässrige Emulsion von (a.1 ) aus Beispiel 1.130 g / l aqueous emulsion of (a.1) from Example 1.1
1 g/l 1-Hexanolethoxylat (5 Mol Ethylenoxid/mol n-Hexanol), frei von n-Hexanol,1 g / l 1-hexanol ethoxylate (5 mol ethylene oxide / mol n-hexanol), free of n-hexanol,
0,5 g/l Essigsäure, der Rest war Wasser. Danach wurde für 5 Minuten bei 120°C getrocknet. Man erhielt erfindungsgemäßes0.5 g / l acetic acid, the remainder was water. It was then dried for 5 minutes at 120 ° C. The invention was obtained
Textil T1.Textile T1.
Die Einsinkzeit für einen Tropfen destilliertes Wasser betrug 8 Sekunden (nicht behandeltes Textil) bzw. weniger als 0,5 Sekunden (erfindungsgemäßes Textil T1 ).
11.1 Herstellung von erfindungsgemäßem Textil T2The sink-in time for one drop of distilled water was 8 seconds (untreated fabric) or less than 0.5 seconds (fabric T1 according to the invention). 11.1 Production of Textile T2 According to the Invention
Ein Polypropylenvlies (100 % Polypropylen, Flächengewicht 90 g/m2) wurde mit einer wässrigen Formulierung foulardiert, bestehend ausA polypropylene nonwoven (100% polypropylene, basis weight 90 g / m 2 ) was padded with an aqueous formulation consisting of
150 g/l Ethylencopolymer (b.1 ) in wässriger Dispersion, Feststoffgehalt 25%, neutralisiert mit NH3 (mittlerer Teilchendurchmesser (Zahlenmittel) ca. 70 nm) mit den folgenden analytischen Daten:150 g / l of ethylene copolymer (b.1) in aqueous dispersion, solids content 25%, neutralized with NH 3 (average particle diameter (number average) about 70 nm) with the following analytical data:
30 g/l wässrige Emulsion von (a.2) aus 1.230 g / l aqueous emulsion of (a.2) from 1.2
2 g/l 1-Hexanolethoxylat (5 Mol Ethylenoxid/mol n-Hexanol), frei von n-Hexanol, 0,5 g/l Essigsäure, der Rest war Wasser.2 g / l 1-hexanol ethoxylate (5 mol ethylene oxide / mol n-hexanol), free from n-hexanol, 0.5 g / l acetic acid, the remainder was water.
Die Flottenaufnahme beträgt ca. 70%. Danach wurde bei 100°C für 5 Minuten getrocknet, danach für 1 Minute bei 1 10°C fixiert. Man erhielt erfindungsgemäßes Textil T2.The fleet intake is about 70%. It was then dried at 100 ° C for 5 minutes, then fixed at 1 10 ° C for 1 minute. Inventive textile T2 was obtained.
Die Einsinkzeit für einen Wassertropfen betrug > 30 Sekunden (nicht behandeltes Textil) bzw. < 0,5 Sekunden (erfindungsgemäßes Textil T2).
The sink-in time for a water drop was> 30 seconds (untreated textile) or <0.5 seconds (textile T2 according to the invention).
Claims
1. Verfahren zum Behandeln von Textilien aus Polypropylen, dadurch gekennzeichnet, dass man sie mit einer Emulgator-freien wässrigen Formulierung be- handelt, die enthält1. A process for treating textiles made of polypropylene, characterized in that it is treated with an emulsifier-free aqueous formulation containing
(a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe oder(a) at least one silicone compound having at least one hydrophilic group or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Di- carbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or di-carboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei Textilien aus Polypropylen um fadenförmige oder flächige Gebilde aus Polypropylen handelt.2. The method according to claim 1, characterized in that it is textiles made of polypropylene thread-like or planar structure made of polypropylene.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei Silikonverbindung (a) um eine Silikonverbindung handelt, die mindestens eine NH-Gruppe oder mindestens eine C-OH-Gruppe oder mindestens eine Alkylen- oxideinheit pro Molekül aufweist.3. The method according to claim 1 or 2, characterized in that it is silicone compound (a) is a silicone compound having at least one NH group or at least one C-OH group or at least one alkylene oxide unit per molecule.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei Ethylencopolymer (b) um ein Copolymer von Ethylen mit (Meth)acrylsäure handelt.4. The method according to any one of claims 1 to 3, characterized in that it is ethylene copolymer (b) is a copolymer of ethylene with (meth) acrylic acid.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei Polyacrylat (c) um ein Homopolymer von (Meth)acrylsäure handelt oder ein Copolymer von Acrylsäure mit Methacrylsäure oder um ein Copolymer von (Meth)acrylsäure mit einem oder mehreren Ci-Cio-Alkylacrylaten oder einem5. The method according to any one of claims 1 to 4, characterized in that polyacrylate (c) is a homopolymer of (meth) acrylic acid or a copolymer of acrylic acid with methacrylic acid or a copolymer of (meth) acrylic acid with one or a plurality of Ci-Cio-alkyl acrylates or a
Polyethylenoxidester der (Meth)acrylsäure.Polyethylene oxide ester of (meth) acrylic acid.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Emulgator-freie wässrige Formulierung weniger als 0,1 Gew.-% kationi- sehen, anionischen und nichtionischen Emulgator mit einem Molekulargewicht von bis zu 400 g/mol enthält, bezogen auf die gesamte wässrige Formulierung.6. The method according to any one of claims 1 to 5, characterized in that the emulsifier-free aqueous formulation see less than 0.1 wt .-% cationic, anionic and nonionic emulsifier having a molecular weight of up to 400 g / mol, based on the total aqueous formulation.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man im Anschluss an die Behandlung mit wässriger Formulierung thermisch behandelt. 7. The method according to any one of claims 1 to 6, characterized in that it is treated thermally after the treatment with aqueous formulation.
8. Textilien aus Polypropylen, behandelt nach einem Verfahren nach einem der Ansprüche 1 bis 7.8. textiles made of polypropylene, treated by a method according to any one of claims 1 to 7.
9. Hygienevliese, Bekleidungstextilien und Geotextilien, enthaltend oder beste- hend aus mindestens einem Textil nach Anspruch 8.9. Hygiene mats, clothing textiles and geotextiles, containing or consisting of at least one textile according to claim 8.
10. Baumaterialien, enthaltend mindestens ein Textil nach Anspruch 8.10. Building materials, containing at least one textile according to claim 8.
1 1. Wässrige Formulierung, enthaltend (a) mindestens eine Silikonverbindung mit mindestens einer hydrophilen Gruppe oder1 1. Aqueous formulation comprising (a) at least one silicone compound having at least one hydrophilic group or
(b) mindestens ein Ethylencopolymer, das erhältlich ist durch Copolymerisation von Ethylen mit mindestens einer ethylenisch ungesättigten Mono- oder Di- carbonsäure oder einem Anhydrid einer ethylenisch ungesättigten Mono- oder Dicarbonsäure.(B) at least one ethylene copolymer obtainable by copolymerization of ethylene with at least one ethylenically unsaturated mono- or di-carboxylic acid or an anhydride of an ethylenically unsaturated mono- or dicarboxylic acid.
12. Verwendung von Silikonverbindungen mit mindestens einer NH-Gruppe zum Hydrophilieren von Textilien aus Polypropylen. 12. Use of silicone compounds having at least one NH group for hydrophilizing textiles made of polypropylene.
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EP07704213A EP1984557A2 (en) | 2006-02-09 | 2007-01-30 | Method for treating polypropylene textiles |
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PCT/EP2007/050860 WO2007090758A2 (en) | 2006-02-09 | 2007-01-30 | Method for treating polypropylene textiles |
EP07704213A EP1984557A2 (en) | 2006-02-09 | 2007-01-30 | Method for treating polypropylene textiles |
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US (1) | US20090023834A1 (en) |
EP (1) | EP1984557A2 (en) |
AU (1) | AU2007213841A1 (en) |
CA (1) | CA2637772A1 (en) |
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US4753840A (en) * | 1985-01-10 | 1988-06-28 | Kimberly-Clark Corporation | Coated fabric |
CN1141089A (en) * | 1994-01-07 | 1997-01-22 | 美国3M公司 | An electrostatic toner receptor layer of rubber modified thermoplastic |
US5908663A (en) * | 1996-02-01 | 1999-06-01 | Minnesota Mining And Manufacturing Company | Topical carpet treatment |
US5728502A (en) * | 1996-03-12 | 1998-03-17 | Minnesota Mining And Manufacturing Company | Imaging medium, method of imaging said medium, and image-bearing medium |
JP3362348B2 (en) * | 1996-05-15 | 2003-01-07 | 旭化成株式会社 | Polyolefin nonwoven fabric for sanitary materials |
JP3313284B2 (en) * | 1996-08-02 | 2002-08-12 | 旭化成株式会社 | Polyolefin-based nonwoven fabric with hydrophilic treatment agent |
US6153701A (en) * | 1998-11-20 | 2000-11-28 | International Paper Company | Wettable polypropylene composition and related method of manufacture |
DE10132884A1 (en) * | 2001-07-06 | 2003-01-16 | Buelent Oez | Process for printing substrates |
KR101002901B1 (en) * | 2003-05-14 | 2010-12-21 | 게에 바이엘 실리콘스 게엠베하 운트 코. 카게 | Polyorganosiloxane compositions for the treatment of substrates |
DE10345798A1 (en) * | 2003-09-30 | 2005-04-14 | Basf Ag | Amino group-containing ethylene copolymer waxes and their use |
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US20090023834A1 (en) | 2009-01-22 |
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