EP0084772B1 - Grafted siloxane dispersions for the finishing of textile materials - Google Patents
Grafted siloxane dispersions for the finishing of textile materials Download PDFInfo
- Publication number
- EP0084772B1 EP0084772B1 EP83100041A EP83100041A EP0084772B1 EP 0084772 B1 EP0084772 B1 EP 0084772B1 EP 83100041 A EP83100041 A EP 83100041A EP 83100041 A EP83100041 A EP 83100041A EP 0084772 B1 EP0084772 B1 EP 0084772B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- vinyl
- textile
- graft
- organopolysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004753 textile Substances 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims description 3
- 239000006185 dispersion Substances 0.000 title description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 41
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000009988 textile finishing Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 20
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 5
- 239000004815 dispersion polymer Substances 0.000 abstract description 2
- -1 polysiloxanes Polymers 0.000 description 40
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 150000002084 enol ethers Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 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 4
- 229920000742 Cotton Polymers 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Chemical group 0.000 description 2
- 229910052739 hydrogen Chemical group 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- PLCFYBDYBCOLSP-UHFFFAOYSA-N tris(prop-2-enyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C=CCOC(=O)CC(O)(CC(=O)OCC=C)C(=O)OCC=C PLCFYBDYBCOLSP-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 description 1
- PQVHMOLNSYFXIJ-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazole-3-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)C(=O)O PQVHMOLNSYFXIJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
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- MIGNWTQKRPNYLP-UHFFFAOYSA-N but-2-ene-2,3-diol urea Chemical compound NC(=O)N.OC(=C(C)O)C MIGNWTQKRPNYLP-UHFFFAOYSA-N 0.000 description 1
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical class CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- BGSFCOHRQUBESL-UHFFFAOYSA-N ethyl prop-2-enyl carbonate Chemical compound CCOC(=O)OCC=C BGSFCOHRQUBESL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ORUWSEKEVGOAQR-UHFFFAOYSA-N phenyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OC1=CC=CC=C1 ORUWSEKEVGOAQR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
Definitions
- the present invention relates to textile finishing agents which contain siloxane graft copolymers.
- Silicones are used in the textile industry as water repellents. Compared to other strongly hydrophobic substances, e.g. As paraffin and waxes, silicones have the advantage that they have no fat character, which has a favorable effect on the "handle" of the treated fabric, that they can be fixed on the fiber in such a way that they can be washed or solvent treated to a comparatively high degree Withstand textiles, that they are largely resistant to chemicals and weather and that they ultimately have a remarkable softening and smoothing effect on the textile, but the softening effect of the silicones has such an effect on some textiles (cotton, polyester, polyamide) that treated textile finally attacks softly and lobularly, which can be undesirable for some applications.
- some textiles cotton, polyester, polyamide
- acrylates or polyacrylates and methacrylates can be used to increase the stiffness of fabrics.
- these products do not give the textiles the desired elasticity and resilience, even when used in combination with silicones.
- the object of the invention is achieved in that special graft copolymers are used to finish textile material.
- graft modification of organopolysiloxanes with vinyl monomers is described, for example, in GB-A-766528, GB-A-806 582, GB-A-869 482 and DE-B-1 694 973. It is also known from US-A-4166 078 to modify Si-H-siloxanes by grafting with vinyl monomers. Furthermore, US-A-4172101 describes the graft modification of vinyl-substituted polysiloxanes.
- the mixtures of polymethylhydrogensiloxanes, vinyl group-containing polysiloxanes and vinyl monomers are subjected to radical polymerization with the addition of radical formers and, if appropriate, molecular weight regulators.
- Stable dispersions are obtained which consist of an organopolysiloxane component and polymerized units of one or more vinyl monomers and which contain graft polymers of organopolysiloxanes which are cross-bridged via polymerized units of the vinyl monomers used, part of the Si-H groups of the polymethylhydrogensiloxanes being modified by monoaddition of the vinyl compounds used.
- graft polymers produced in this way are soluble or dispersible in water; Even with a high silicone content, these polymers can be easily emulsified in water with relatively little emulsifier additives.
- the radical polymerization of the vinyl monomers can be started in a manner known per se with the aid of radical formers, UV rays, a, ⁇ or y rays or thermally without further additives.
- the radiation-initiated polymerization is preferably carried out in the presence of sensitizers, cf. e.g. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, p. 465.
- radical formers are used in amounts between 0.001 to 2, preferably 0.02 to 0.8% by weight, based on the total mixture of organopolysiloxane, radical formers and vinyl monomers.
- Azo initiators such as azobis-isobutyronitrile (AIBN), azo esters, azo imino esters or azo-N-alkyl amides, peroxides such as di-tert-butyl peroxide, di-cumyl peroxide, di-benzoyl peroxide, peresters such as amyl perpivalate, tert .-Butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, percarbonates such as cyclohexyl percarbonate or bisisopropyl percarbonate or hydroperoxides such as Cumyl hydroperoxide,
- AIBN azobis-isobutyroni
- Suitable initiators are also benzpinacol, benzpinacol derivatives or other thermally labile, highly substituted ethane derivatives.
- the polymerization can also be started with the help of redox systems at temperatures lower than the purely thermal decomposition temperatures of the radical formers.
- peroxides and amines such as e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-quality transition metal salts and sulfur dioxide / peroxide redox systems.
- the polymerization reaction can be carried out continuously or batchwise, without pressure or at reaction pressures up to, for. B. 300 bar, preferably up to 15 bar, at reaction temperatures between -20 ° C and + 250 ° C, preferably 70 to 190 ° C.
- the polymerization can also be carried out in the presence of solvents or diluents, water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or tetrahydrofuran, Esters such as Ethyl acetate.
- solvents or diluents water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or tetrahydr
- the polymerization reaction can be carried out in the presence of molecular weight regulators.
- molecular weight regulators such as Mercaptans such as n- or tert-dodecyl mercaptan, thioglycol, thioglycerol or thioacetic acid esters may be mentioned as regulators.
- sulfur-free molecular weight regulators such as hydrocarbons, examples include paraffin fractions such as. As petroleum ether, light or white spirit, a-olefins such.
- B. propylene, isobutylene, butene-1, furthermore ketones such. As acetone, methyl ethyl ketone or cyclohexanone, also aldehydes such as. B.
- allyl ethers which are derived on the one hand from aliphatic or cycloaliphatic aldehydes or ketones and on the other hand from alkyl, cycloalkyl or aralkyl alcohols are suitable for the process.
- the cycloaliphatic aldehydes or ketones can be substituted or bridged in the ring and / or contain a double bond.
- Examples include butyraldehyde, valeraldehyde, cyclohexylaldehyde, cyclohexenylaldehyde, bicyclo [2,2,1] hexenylaldehyde and cyclohexanone.
- Preferred are the cycloaliphatic aldehydes or ketones, which are optionally substituted by one or two C, -C, alkyl groups, in particular by methyl groups in the ring.
- Suitable alcohols are C 1 -C 20 alkanols, which optionally may be branched or unsaturated and C 5 -C 10 cycloalkanols and Cy-C zo -Aralkylalkohole whose cycloalkyl or aryl group may be optionally substituted by lower alkyl radicals.
- Examples include methanol, ethanol, n-propanol, isobutanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
- the enol ethers used as molecular weight regulators are used in amounts of 0.01-10% by weight, preferably 0.05-1% by weight, based on the sum of the monomers.
- the enol ethers can be added at any time during the polymerization, preferably the enol ether used as regulator is added at the beginning of the polymerization.
- Also suitable as telogens are halogenated hydrocarbons such as methylene chloride, tetrachloroethane, dibromoethane, etc. As expected, the viscosities of the dispersions can be controlled with the aid of such regulators.
- the graft polymers can be prepared by bringing mixtures of a terminally vinyl-functional organopolysiloxane, a methylhydrogenpolysiloxane and one or more vinyl monomers in the presence of a radical generator to a reaction temperature which triggers the polymerization. If desired, mixtures of terminally vinyl-functional and non-functional organopolysiloxanes can also be introduced into the reaction mixture.
- the polymerization can be carried out by a continuous or batch process. In principle, the order of addition of the components to be reacted is arbitrary, but the best results are achieved if mixtures of vinylsiloxane and hydrogen siloxane and vinyl monomers are used simultaneously in the course of the polymerization reaction.
- the conversion of the monomers used is determined by the chosen polymerization process and the reaction conditions. In the batchwise polymerization mode, the highest possible conversions are aimed at, so that at least 80% of the monomers used, but preferably more than 90%, are converted.
- the residual monomers are removed by known methods by distillation at normal pressure or under reduced pressure. The residual monomer contents which were effectively found in the dispersions after working up are negligibly low, they are generally below 1,000 ppm, preferably below 100 ppm.
- This monoaddition changes the polarity and hydrophobicity of the polysiloxane chain and improves the interaction with the textile substrate.
- the silicone-vinyl polymer! Sates according to the invention are particularly suitable for the coating and finishing of natural or synthetic fibers, threads or textile fabrics. They give textile articles both the voluminous soft feel that is characteristic of silicone, as well as permanent elasticity and resilience.
- the silicone-vinyl polymers according to the invention have an emulsifying behavior which is comparatively more favorable than that of pure silicones of corresponding viscosity.
- the emulsifiers used expediently consist of a mixture of a hydrophilic and a hydrophobic component.
- Suitable compounds are, for example, fatty acid esters of polyhydric alcohols, such as stearic acid esters of glycols, glycerol or sorbitol, as well as higher fatty alcohols or the adducts of ethylene oxide with these fatty alcohols, fatty acids or similar compounds with an active hydrogen atom.
- anion-active emulsifiers such as sodium lauryl sulfate or sodium dodecylbenzenesulfonate or cation-active emulsifiers such as quaternary ammonium compounds are also suitable.
- silicone-vinyl copolymers according to the invention are applied to the substrate to be treated by the known methods, for example by padding, drying and condensing, by spraying or slapping.
- the silicone graft polymer component can be thermally or catalytically crosslinked, if appropriate with the addition of further reactive silicone derivatives such as e.g. Polymethylhydrogensiloxanen done.
- the purely thermal crosslinking takes place at temperatures from around 120 ° C.
- the catalytically activated crosslinking can take place at room temperature.
- Known systems such as platinum or platinum compounds, organotin compounds but also peroxides or other radical initiators are suitable as catalysts.
- UV-activated crosslinking can also be carried out successfully. Crosslinking improves the solvent and wash resistance of the equipment. In the case of catalytic crosslinking, it is advisable to use appropriate inhibitors, such as Use acetylene alcohols, especially methylenedinol.
- the polydiorganosiloxanes are prepared in a manner known per se (cf. W. Noll, “Chemistry and Technology of Silicones”, Verlag Chemie, Weinheim / Bergstrasse, 2nd ed., 1968, chap. 5, p. 162 ff.).
- siloxanes listed in the examples are identified as follows:
- the mixture is stirred for 1 hour and then the volatile constituents are removed by distillation.
- the mixture is stirred at 150 ° C. for 1 hour, then evacuated and virtually completely freed of unreacted monomers.
- the graft polymer obtained has a viscosity of 1500 mPas at 25 ° C. and has a composition which corresponds to an 88% monomer conversion.
- the application takes place in the manner described above.
- DMDHEU dimethyldihydroxyethylene urea
- acrylate dispersions and plasticizers based on fatty acid amides and / or silicones are added to the finishing liquor.
- the application is carried out by diving (picking up liquor 70-100% of the weight of the goods), squeezing and then drying. This is followed by a calendering and condensation step at 140-160 ° C for 4 to 6 minutes.
- Example 11 In comparison to Example 11, the advantageous handle, tear resistance and crease angle remain practically unchanged in Example 15 according to the invention even after 5 washes at 60 ° C., while Example 11 after 5 washes under the same conditions shows significant deteriorations in the handle (rough, empty) and significant reduction of tear resistance and crease angle.
- a 100% co-circular knitted fabric (100 kg) structured in the longitudinal direction is dyed with reactive dyes on a nozzle dyeing machine, rinsed hot and cold several times and soaped at cooking temperature; so that all unfixed dye components are removed.
- the last rinsing bath remains in the machine.
- 2 kg of the graft copolymer according to the invention from Example 4 (corresponds to 2% of the total weight) are passed through a batch vessel.
- the pH of the rinsing liquor was previously adjusted to 6.0 with acetic acid.
- the treatment bath is at 1 ° C / min. heated to 35 ° C. After reaching the final temperature, the goods remain for 15 minutes. in the equipment fleet.
- the liquor is then drained off, the goods are removed from the dyeing apparatus and dried continuously at 125 ° C.
- the handle of the treated goods is full, soft and smooth.
- the test serves to determine the elongation and the resilience (resilience) of textile fabrics under certain static tensile loads with subsequent relief.
- 3 strip-shaped samples 300 mm long and 50 mm wide are taken from the textile fabrics to be tested in the warp and weft directions, and in knitted fabrics in the longitudinal and transverse directions.
- the samples are clamped in an upper fixed and a lower movable clamping clamp so that 50 mm protrude from the upper and lower clamp.
- the middle 100 mm are identified as the measuring section.
- a weight is attached to the lower clamp, which together with the weight of the clamp results in a test force of 25 N (2.5 Kp).
- the elongation of the test specimen is measured and the static elongation in% is calculated from the change in length.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Silicon Compounds (AREA)
- Pens And Brushes (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft Textilausrüstungsmittel, die Siloxanpfropfcopolymerisate enthalten.The present invention relates to textile finishing agents which contain siloxane graft copolymers.
Silicone werden in der Textilindustrie als Hydrophobiermittel verwendet. Gegenüber anderen stark hydrophoben Substanzen, z. B. Paraffin und Wachsen, besitzen Silicone den Vorteil, dass sie keinen Fettcharakter haben, was sich günstig auf den «Griff" des behandelten Gewebes auswirkt; dass sie auf der Faser derart fixierbar sind, dass sie in vergleichsweise hohem Masse einer Wäsche oder Lösungsmittelbehandlung des Textils standhalten; dass sie weitgehend chemikalien-und witterungsbeständig sind und schliesslich auf das Textil eine recht beachtliche weichmachende und glättende Wirkung ausüben. Der weichmachende Effekt der Silicone wirkt sich auf einigen Textilien (Baumwolle, Polyester, Polyamid) jedoch so stark aus, dass sich das behandelte Textil schliesslich weich und lappig angreift, was für manche Anwendungen unerwünscht sein kann.Silicones are used in the textile industry as water repellents. Compared to other strongly hydrophobic substances, e.g. As paraffin and waxes, silicones have the advantage that they have no fat character, which has a favorable effect on the "handle" of the treated fabric, that they can be fixed on the fiber in such a way that they can be washed or solvent treated to a comparatively high degree Withstand textiles, that they are largely resistant to chemicals and weather and that they ultimately have a remarkable softening and smoothing effect on the textile, but the softening effect of the silicones has such an effect on some textiles (cotton, polyester, polyamide) that treated textile finally attacks softly and lobularly, which can be undesirable for some applications.
Vielmehr werden Rückstellvermögen und eine gewisse Elastizität des behandelten Gewebes gefordert.Rather, resilience and a certain elasticity of the treated tissue are required.
Nach dem Stand der Technik kann man zur Erhöhung der Steifigkeit von Geweben Acrylate bzw. Polyacrylate und -Methacrylate einsetzen. Diese Produkte verleihen den Textilien aber nicht die erwünschte Elastizität und das Rückstellvermögen, auch dann nicht, wenn man sie in Kombination mit Siliconen anwendet.According to the prior art, acrylates or polyacrylates and methacrylates can be used to increase the stiffness of fabrics. However, these products do not give the textiles the desired elasticity and resilience, even when used in combination with silicones.
Es war daher Aufgabe der vorliegenden Erfindung, Ausrüstungsmittel zu entwickeln, die textilen flächigen oder faserigen Gebilden sowohl Sprungelastizität als auch ein gewisses Rückstellvermögen bei gleichzeitiger weicher und volumiger Griffgebung verleihen.It was therefore an object of the present invention to develop finishing agents which give textile flat or fibrous structures both resilience and a certain resilience with a soft and voluminous feel at the same time.
Die erfindungsgemässe Aufgabe wird dadurch gelöst, dass man zur Ausrüstung von textilem Material spezielle Pfropfcopolymere einsetzt.The object of the invention is achieved in that special graft copolymers are used to finish textile material.
Gegenstand der vorliegenden Erfindung sind somit Textilausrüstungsmittel, enthaltend ein Pfropfcopolymerisat bestehend aus
- A. einem vinylgruppenhaltigen Diorganopolysiloxan
- B. einem Organo-Hydrogen-Polysiloxan und
- C. polymerisierten Einheiten aus ein- oder mehrfach olefinisch ungesättigten Verbindungen vom Vinyl-Typ,
wobei ein Teil der Organopolysiloxankomponenten (A) über polymerisierte Einheiten der eingesetzten Vinylmonomeren verknüpft ist und ein Teil der Si-H-Gruppen des Si-H-Organopolysiloxans (B) durch Monoaddition der eingesetzten Vinylverbindungen modifiziert ist.The present invention thus relates to textile finishing agents comprising a graft copolymer consisting of
- A. a vinyl group-containing diorganopolysiloxane
- B. an organohydrogen polysiloxane and
- C. polymerized units of mono- or poly-olefinically unsaturated compounds of the vinyl type,
where part of the organopolysiloxane components (A) is linked via polymerized units of the vinyl monomers used and part of the Si-H groups of the Si-H organopolysiloxane (B) is modified by monoaddition of the vinyl compounds used.
Die Pfropfmodifizierung von Organopolysiloxanen mit Vinylmonomeren wird beispielsweise in den Patentschriften GB-A-766528, GB-A-806 582, GB-A-869 482 und DE-B-1 694 973 beschrieben. Ferner ist aus US-A-4166 078 bekannt, Si-H-Siloxane durch Pfropfung mit Vinylmonomeren zu modifizieren. Weiterhin wird in US-A-4172101 die Pfropfmodifizierung von vinylsubstituierten Polysiloxanen beschrieben.The graft modification of organopolysiloxanes with vinyl monomers is described, for example, in GB-A-766528, GB-A-806 582, GB-A-869 482 and DE-B-1 694 973. It is also known from US-A-4166 078 to modify Si-H-siloxanes by grafting with vinyl monomers. Furthermore, US-A-4172101 describes the graft modification of vinyl-substituted polysiloxanes.
Ferner wird in W. Noll «Chemie und Technologie der Silicone»; Verlag Chemie, Weinheim, Bergstr. 2. Auflage (1968), S. 341 beschrieben, dass durch Kombination von Si-H-Siloxanen mit Si-Vinylsiloxanen in Gegenwart von Radikalbildnern vernetzte Produkte erhalten werden. Überraschenderweise wurde gefunden, dass bei der radikalischen Polymerisation von Vinylmonomeren in Gegenwart von Mischungen aus Si-H-Siloxanen und Si-Vinylsiloxanen unvernetzte, zum Teil niedrigviskose Pfropfpolymerisate erhalten werden.W. Noll also discusses “Chemistry and Technology of Silicones”; Verlag Chemie, Weinheim, Bergstr. 2nd edition (1968), p. 341 describes that crosslinked products are obtained by combining Si-H-siloxanes with Si-vinylsiloxanes in the presence of radical formers. Surprisingly, it was found that in the free-radical polymerization of vinyl monomers in the presence of mixtures of Si-H-siloxanes and Si-vinylsiloxanes, uncrosslinked, partly low-viscosity graft polymers are obtained.
Unter den erfindungsgemässen Textilausrüstungsmitteln sind solche besonders geeignet, die aus folgenden Komponenten aufgebaut sind:
- A) vinylgruppenhaltige Polysiloxane der Formel
- R' ausgewählt ist aus Alkylresten mit 1 bis 32 Kohlenstoffatomen, Arylreste, Vinylresten und Fluoralkylresten mit 3 bis 18 Kohlenstoffatomen, so dass das Polymer 0.0002 bis 3 Gew.-% Vinyl enthält und c einen Wert hat, dass die Viskosität des Polymers von 100 bis 1 000000 mPa. s bei 25°C variiert.
- B) Polymethylhydrogensiloxane der allgemeinen Formel
- a eine ganze Zahl zwischen 1 und 120,
- b eine ganze Zahl zwischen 0 und 140 und
- X eine Methylgruppe oder Wasserstoff bedeutet.
- C) Vinylmonomere, für die beispielhaft aufgeführt seien:
- Olefine wie Ethylen, Propylen, Isobutylen, Vinylester aliphatischer oder aromatischer Carbonsäuren, vorzugsweise Vinylacetat, Vinylpropionat, a,ß-ungesättigte Mono- oder Dicarbonsäuren und ihre Derivate, erwähnt seien (Meth)acrylsäure, Methyl(meth)acrylat, Ethyl(meth)acrylat, Propyl- bzw. isopropyl(meth)acrylat, n-Butyl-, iso- oder tert.-Butyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, (Meth)acrylamidderivate, quaternisierte (Meth)Acrylamidderivate, (Meth)acrylnitril, Maleinsäureanhydrid, Maleinsäureamid, N-Alkyl-Maleinamide und -imide, Maleinsäure-halb- oder -diester, Vinylaromaten wie Styrol, a-Methylstyrol, 4-Chlorstyrol, Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid, Tetrafluorethylen, Vinylether wie Ethylvinylether oder n-Butylvinylether; aus der Reihe der Allylverbindungen seien angeführt Alkylalkohol, Allylacetat, Isobutendiacetat, 2-Methylenpropandiol-1,3, Allylethylcarbonat, Allylphenylcarbonat. Falls die Vernetzung oder Erhöhung der Molekulargewichte der Vinylharzphase gewünscht wird, können mehrfach ungesättigte Vinylverbindungen oder Allylverbindungen eingesetzt werden. Erwähnt seien Divinylbenzol, (Meth)Acrylsäureester mehrwertiger Alkohole wie z. B. Ethylenglykoldimethacrylat, Diethylenglykoldiacrylat und Divinylether, ferner Triallylcyanurat, Triallylcitrat.
- A) vinyl group-containing polysiloxanes of the formula
- R 'is selected from alkyl radicals with 1 to 32 carbon atoms, aryl radicals, vinyl radicals and fluoroalkyl radicals with 3 to 18 carbon atoms, so that the polymer contains 0.0002 to 3% by weight of vinyl and c has a value such that the viscosity of the polymer is from 100 to 1 000 000 mPa. s varies at 25 ° C.
- B) polymethylhydrogensiloxanes of the general formula
- a is an integer between 1 and 120,
- b is an integer between 0 and 140 and
- X represents a methyl group or hydrogen.
- C) vinyl monomers, examples of which are:
- Olefins such as ethylene, propylene, isobutylene, vinyl esters of aliphatic or aromatic carboxylic acids, preferably vinyl acetate, vinyl propionate, α, β-unsaturated mono- or dicarboxylic acids and their derivatives, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate may be mentioned , Propyl or isopropyl (meth) acrylate, n-butyl, iso- or tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylamide derivatives, quaternized (meth) acrylamide derivatives, (meth) acrylonitrile, maleic anhydride, maleic amide, N-alkyl-maleinamides and imides, maleic acid semiester or diesters, vinyl aromatics such as styrene, a-methylstyrene, 4-chlorostyrene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, vinyl ethers such as ethyl vinyl ether or n-butyl vinyl ether ; Al. from the series of allyl compounds alkyl alcohol, allyl acetate, isobutene diacetate, 2-methylene-propanediol-1,3, allyl ethyl carbonate, allyl phenyl carbonate. If it is desired to crosslink or increase the molecular weights of the vinyl resin phase, polyunsaturated vinyl compounds or allyl compounds can be used. Mention should be made of divinylbenzene, (meth) acrylic esters of polyhydric alcohols such as. B. ethylene glycol dimethacrylate, diethylene glycol diacrylate and divinyl ether, also triallyl cyanurate, triallyl citrate.
Die Mischungen aus Polymethylhydrogensiloxanen, vinylgruppenhaltigen Polysiloxanen und Vinylmonomeren werden unter Zusatz von Radikalbildnern und gegebenenfalls Molekulargewichtsreglern einer radikalischen Polymerisation unterzogen. Man erhält stabile Dispersionen, die aus einer Organopolysiloxankomponente und polymerisierten Einheiten eines oder mehrerer Vinylmonomerer bestehen und die über polymerisierte Einheiten der eingesetzten Vinylmonomeren querverbrückte Pfropfpolymere aus Organopolysiloxanen enthalten, wobei ein Teil der Si-H-Gruppen der Polymethylhydrogensiloxane durch Monoaddition der eingesetzten Vinylverbindungen modifiziert ist. Solchermassen hergestellte Pfropfpolymere sind, je nach Zusammensetzung, in Wasser löslich oder dispergierbar; auch bei hohem Silicongehalt lassen sich diese Polymeren durch relativ wenig Emulgatorzusätze leicht in Wasser emulgieren.The mixtures of polymethylhydrogensiloxanes, vinyl group-containing polysiloxanes and vinyl monomers are subjected to radical polymerization with the addition of radical formers and, if appropriate, molecular weight regulators. Stable dispersions are obtained which consist of an organopolysiloxane component and polymerized units of one or more vinyl monomers and which contain graft polymers of organopolysiloxanes which are cross-bridged via polymerized units of the vinyl monomers used, part of the Si-H groups of the polymethylhydrogensiloxanes being modified by monoaddition of the vinyl compounds used. Depending on the composition, graft polymers produced in this way are soluble or dispersible in water; Even with a high silicone content, these polymers can be easily emulsified in water with relatively little emulsifier additives.
Die erfindungsgemäss verwendeten wasserlöslichen oder wasserdispergierbaren Organopolysiloxan-Pfropfpolymeren bestehen insbesondere aus:
- 1. 15 bis 95 Gew.-% eines Pfropfsubstrates, bestehend aus
- A. 5 bis 95 Gew.-% Vinylgruppen enthaltenden Diorganopolysiloxan und
- B. 5 bis 95 Gew.-% Methylhydrogenpolysiloxan und
- 2. 85 bis 5 Gew.-% polymerisierten Einheiten aus Vinylverbindungen,
wobei die Summe der Komponenten 1. und 2. stets 100% beträgt.The water-soluble or water-dispersible organopolysiloxane graft polymers used according to the invention consist in particular of:
- 1. 15 to 95 wt .-% of a graft substrate consisting of
- A. 5 to 95 wt .-% vinyl groups containing diorganopolysiloxane and
- B. 5 to 95 wt .-% methylhydrogenpolysiloxane and
- 2. 85 to 5% by weight of polymerized units of vinyl compounds,
the sum of components 1. and 2. is always 100%.
Vorzugsweise enthalten die erfindungsgemässen Polysiloxanzubereitungen ein Pfropfcopolymerisat aus
- 1. 40-90 Gew.-% eines Pfropfsubstrates bestehend aus
- a) 20-80 Gew.-% Vinylgruppen enthaltenden Diorganopolysiloxan
- b) 80-20 Gew.-% Polymethylhydrogensiloxan und
- 2. als zumindest teilweise aufgepfropfte Polymerphase 60 bis 10 Gew.-% polymerisierten Einheiten aus n-Butylacrylat
wobei die Summe der Komponenten stets 100 Gew.-% beträgt.The polysiloxane preparations according to the invention preferably contain a graft copolymer
- 1. 40-90 wt .-% of a graft substrate consisting of
- a) 20-80% by weight of vinyl groups-containing diorganopolysiloxane
- b) 80-20% by weight of polymethylhydrogensiloxane and
- 2. 60 to 10% by weight of polymerized units of n-butyl acrylate as the at least partially grafted polymer phase
the sum of the components always being 100% by weight.
Die radikalische Polymerisation der Vinylmonomeren kann in an und für sich bekannter Weise mit Hilfe von Radikalbildnern, UV-Strahlen, a-, β- oder y-Strahlen oder thermisch ohne weitere Zusätze gestartet werden. Die strahlungsinitiierte Polymerisation wird vorzugsweise in Gegenwart von Sensibilisatoren durchgeführt, vgl. z.B. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, S. 465.The radical polymerization of the vinyl monomers can be started in a manner known per se with the aid of radical formers, UV rays, a, β or y rays or thermally without further additives. The radiation-initiated polymerization is preferably carried out in the presence of sensitizers, cf. e.g. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, p. 465.
Um die radikalische Polymerisation der Vinylmonomeren zu starten, werden Radikalbildner in Mengen zwischen 0,001 bis 2, vorzugsweise 0,02 bis 0,8 Gew.-% bezogen auf die Gesamtmischung aus Organopolysiloxan, Radikalbildner und Vinylmonomeren eingesetzt. Als Radikalbildner seien beispielhaft aufgeführt Azo-Initiatoren wie Azobis-iso-buttersäurenitril (AIBN), Azoester, Azo-Iminoester oder Azo-N-Alkylamide, Peroxide wie di-tert.-Butylperoxid, di-Cumylperoxid, diBenzoylperoxid, Perester wie Amylperpivalat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperbenzoat, tert.-Butylperneodecanoat, Percarbonate wie Cyclohexylpercarbonat oder Bisisopropylpercarbonat oder Hydroperoxide wie z.B. Cumylhydroperoxid, tert.-Butylhydroperoxid.In order to start the radical polymerization of the vinyl monomers, radical formers are used in amounts between 0.001 to 2, preferably 0.02 to 0.8% by weight, based on the total mixture of organopolysiloxane, radical formers and vinyl monomers. Azo initiators such as azobis-isobutyronitrile (AIBN), azo esters, azo imino esters or azo-N-alkyl amides, peroxides such as di-tert-butyl peroxide, di-cumyl peroxide, di-benzoyl peroxide, peresters such as amyl perpivalate, tert .-Butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, percarbonates such as cyclohexyl percarbonate or bisisopropyl percarbonate or hydroperoxides such as Cumyl hydroperoxide, tert-butyl hydroperoxide.
Geeignete Initiatoren sind ferner Benzpinakol, Benzpinakolderivate oder andere thermisch labile hochsubstituierte Ethanderivate.Suitable initiators are also benzpinacol, benzpinacol derivatives or other thermally labile, highly substituted ethane derivatives.
Die Polymerisation kann ferner mit Hilfe von Redoxsystemen bei tieferen Temperaturen als den rein thermischen Zerfalltemperaturen der Radikalbildner entspricht, gestartet werden.The polymerization can also be started with the help of redox systems at temperatures lower than the purely thermal decomposition temperatures of the radical formers.
Als Redox-Initiatoren seien beispielhaft erwähnt Kombinationen aus Peroxiden und Aminen, wie z.B. Benzoylperoxid und Triethylamin, Trialkylborverbindungen und Sauerstoff, Hydroperoxide und Sulfinsäuren, Formaldehyd oder Aldosen oder Kombinationen mit niederwertigen Übergangsmetallsalzen und Schwefeldioxid/Peroxid-Redoxsysteme.Combinations of peroxides and amines, such as e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-quality transition metal salts and sulfur dioxide / peroxide redox systems.
Die Polymerisationsreaktion kann kontinuierlich oder diskontinuierlich, drucklos oder bei Reaktionsdrucken bis z. B. 300 bar, vorzugsweise bis 15 bar, bei Reaktionstemperaturen zwischen -20°C und +250°C, vorzugsweise 70 bis 190°C, durchgeführt werden. Falls erwünscht, kann die Polymerisation auch in Gegenwart von Lösungsmitteln oder Verdünnungsmitteln durchgeführt werden, genannt seien Wasser, Alkohole, wie Methanol, Ethanol, tert.-Butanol, aliphatische oder aromatische Kohlenwasserstoffe, HalogenKohlenwasserstoffe wie Chlorbenzol oder fluorierte Verbindungen, Ether wie Dioxan oder Tetrahydrofuran, Ester wie z.B. Essigsäureethylester. Vorzugsweise wird die Polymerisation aber lösungsmittelfrei durchgeführt.The polymerization reaction can be carried out continuously or batchwise, without pressure or at reaction pressures up to, for. B. 300 bar, preferably up to 15 bar, at reaction temperatures between -20 ° C and + 250 ° C, preferably 70 to 190 ° C. If desired, the polymerization can also be carried out in the presence of solvents or diluents, water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or tetrahydrofuran, Esters such as Ethyl acetate. However, the polymerization is preferably carried out without solvents.
Falls gewünscht, kann die Polymerisationsreaktion in Gegenwart von Molekulargewichtsreglern durchgeführt werden. Als Regler seien aufgeführt Mercaptane, wie n- oder tert.-Dodecylmercaptan, Thioglykol, Thioglycerin oder Thioessigsäureester. Ferner schwefelfreie Molekulargewichtsregler wie Kohlenwasserstoffe, beispielhaft seien genannt Paraffinfraktionen wie z. B. Petrolether, Leicht- oder Waschbenzin, a-Olefine wie z. B. Propylen, Isobutylen, Buten-1, ferner Ketone wie z. B. Aceton, Methylethylketon oder Cyclohexanon, ferner Aldehyde wie z. B. Formaldehyd, Acetaldehyd, Propionaldehyd, Isobutyraldehyd oder Allylverbindungen wie z.B. Allylalkohol, Allylacetat, lsobutendiacetat oder Allylcarbonate. Für das Verfahren sind Enolether geeignet, die sich einerseits von aliphatischen oder cycloaliphatischen Aldehyden oder Ketonen und andererseits von Alkyl-, Cycloalkyl- oder Aralkylalkoholen ableiten. Die cycloaliphatischen Aldehyde oder Ketone können im Ring substituiert oder überbrückt sein und/ oder eine Doppelbindung enthalten. Beispielhaft seien Butyraldehyd, Valeraldehyd, Cyclohexylaldehyd, Cyclohexenylaldehyd, Bicyclo-[2,2,1]-hexenylaldehyd und Cyclohexanon genannt. Bevorzugt sind die cycloaliphatischen Aldehyde oder Ketone, die gegebenenfalls durch eine oder zwei C,-C,-Alkylgruppen, insbesondere durch Methylgruppen im Ring substituiert sind.If desired, the polymerization reaction can be carried out in the presence of molecular weight regulators. Mercaptans such as n- or tert-dodecyl mercaptan, thioglycol, thioglycerol or thioacetic acid esters may be mentioned as regulators. Furthermore, sulfur-free molecular weight regulators such as hydrocarbons, examples include paraffin fractions such as. As petroleum ether, light or white spirit, a-olefins such. B. propylene, isobutylene, butene-1, furthermore ketones such. As acetone, methyl ethyl ketone or cyclohexanone, also aldehydes such as. B. formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde or allyl compounds such as allyl alcohol, allyl acetate, iso butenediacetate or allyl carbonates. Enol ethers which are derived on the one hand from aliphatic or cycloaliphatic aldehydes or ketones and on the other hand from alkyl, cycloalkyl or aralkyl alcohols are suitable for the process. The cycloaliphatic aldehydes or ketones can be substituted or bridged in the ring and / or contain a double bond. Examples include butyraldehyde, valeraldehyde, cyclohexylaldehyde, cyclohexenylaldehyde, bicyclo [2,2,1] hexenylaldehyde and cyclohexanone. Preferred are the cycloaliphatic aldehydes or ketones, which are optionally substituted by one or two C, -C, alkyl groups, in particular by methyl groups in the ring.
Geeignete Alkohole sind C1-C20-Alkanole, die gegebenenfalls verzweigt oder ungesättigt sein können, sowie C5-C10 Cycloalkanole und Cy-Czo-Aralkylalkohole, deren Cycloalkyl- bzw. Arylgruppe gegebenenfalls durch niedere Alkylreste substituiert sein können. Als Beispiele seien Methanol, Ethanol, n-Propanol, Isobutanol, 2-Ethylhexanol, Cyclohexanol und Benzylalkohol genannt.Suitable alcohols are C 1 -C 20 alkanols, which optionally may be branched or unsaturated and C 5 -C 10 cycloalkanols and Cy-C zo -Aralkylalkohole whose cycloalkyl or aryl group may be optionally substituted by lower alkyl radicals. Examples include methanol, ethanol, n-propanol, isobutanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
Die Herstellung von Enolethern ist ausführlich in der Literatur beschrieben, zum Beispiel in Houben-Weyl, Methoden der Organischen Chemie, Band VI/3. Seite 90, Georg Thieme Verlag, Stuttgart, 1965.The preparation of enol ethers is described in detail in the literature, for example in Houben-Weyl, Methods of Organic Chemistry, Volume VI / 3. Page 90, Georg Thieme Verlag, Stuttgart, 1965.
Die als Molekulargewichtsregler verwendeten Enolether werden in Mengen von 0,01-10 Gew.-%, vorzugsweise von 0,05-1 Gew.-%, bezogen auf die Summe der Monomeren, eingesetzt. Die Zugabe der Enolether während der Polymerisation kann zu jedem beliebigen Zeitpunkt erfolgen, vorzugsweise wird der als Regler verwendete Enolether zu Beginn der Polymerisation zugesetzt. Als Telogene kommen ferner in Frage Halogenkohlenwasserstoffe wie Methylenchlorid, Tetrachlorethan, Dibromethan usw. Wie zu erwarten, lassen sich mit Hilfe derartiger Regler die Viskositäten der Dispersionen steuern.The enol ethers used as molecular weight regulators are used in amounts of 0.01-10% by weight, preferably 0.05-1% by weight, based on the sum of the monomers. The enol ethers can be added at any time during the polymerization, preferably the enol ether used as regulator is added at the beginning of the polymerization. Also suitable as telogens are halogenated hydrocarbons such as methylene chloride, tetrachloroethane, dibromoethane, etc. As expected, the viscosities of the dispersions can be controlled with the aid of such regulators.
Die Herstellung der Pfropfpolymerisate kann in der Weise erfolgen, dass Mischungen aus einem endständig Vinyl-funktionellen Organopolysiloxan, einem Methylhydrogenpolysiloxan und einem oder mehrerer Vinylmonomerer in Gegenwart eines Radikalbildners auf eine, die Polymerisation auslösende, Reaktionstemperatur gebracht werden. Falls gewünscht, können auch Mischungen aus endständig vinylfunktionellen und nichtfunktionellen Organopolysiloxanen in die Reaktionsmischung eingetragen werden. Die Polymerisation kann nach kontinuierlichem oder diskontinuierlichem Verfahren durchgeführt werden. Im Prinzip ist die Reihenfolge der Zugabe der zur Reaktion zu bringenden Komponenten beliebig, die besten Resultate werden aber erzielt, wenn Mischungen aus Vinylsiloxan- und Hydrogensiloxan und Vinylmonomeren gleichzeitig bei der Durchführung der Polymerisationsreaktion eingesetzt werden.The graft polymers can be prepared by bringing mixtures of a terminally vinyl-functional organopolysiloxane, a methylhydrogenpolysiloxane and one or more vinyl monomers in the presence of a radical generator to a reaction temperature which triggers the polymerization. If desired, mixtures of terminally vinyl-functional and non-functional organopolysiloxanes can also be introduced into the reaction mixture. The polymerization can be carried out by a continuous or batch process. In principle, the order of addition of the components to be reacted is arbitrary, but the best results are achieved if mixtures of vinylsiloxane and hydrogen siloxane and vinyl monomers are used simultaneously in the course of the polymerization reaction.
Die Umsetzung der eingesetzten Monomeren wird vom gewählten Polymerisationsverfahren und den Reaktionsbedingungen bestimmt. Bei der diskontinuierlichen Polymerisationsweise werden möglichst hohe Umsätze angestrebt, so dass mindestens 80% der eingesetzten Monomeren, vorzugsweise aber mehr als 90% umgesetzt werden. Die Entfernung der Restmonomeren erfolgt nach bekannten Verfahren destillativ bei Normaldruck oder unter vermindertem Druck. Die nach der Aufarbeitung in den Dispersionen noch effektiv gefundenen Restmonomergehalte sind vernachlässigbar gering, sie liegen im allgemeinen unter 1 000 ppm, vorzugsweise unter 100 ppm.The conversion of the monomers used is determined by the chosen polymerization process and the reaction conditions. In the batchwise polymerization mode, the highest possible conversions are aimed at, so that at least 80% of the monomers used, but preferably more than 90%, are converted. The residual monomers are removed by known methods by distillation at normal pressure or under reduced pressure. The residual monomer contents which were effectively found in the dispersions after working up are negligibly low, they are generally below 1,000 ppm, preferably below 100 ppm.
Im Verlaufe der radikalischen Pfropfreaktion findet neben der Polymerisation und Pfropfpolymerisation der Vinylmonomeren auch eine Monoaddition der Vinylmonomeren an die Si-H-Funktion der Methyl-H-Siloxane statt, etwa nach folgendem Reaktionsschema:
Durch diese Monoaddition wird die Polarität und Hydrophobie der Polysiloxankette verändert und die Wechselwirkung mit dem textilen Substrat verbessert.This monoaddition changes the polarity and hydrophobicity of the polysiloxane chain and improves the interaction with the textile substrate.
Die erfindungsgemässen Silicon-Vinylpolymer!- sate sind besonders geeignet für die Beschichtung und die Ausrüstung von natürlichen oder synthetischen Fasern, Fäden oder textilen Flächengebilden. Sie verleihen textilen Gegenständen sowohl den für Silicon charakteristischen voluminösen weichen Griff als auch eine permanente Elastizität und Rückstellvermögen.The silicone-vinyl polymer! Sates according to the invention are particularly suitable for the coating and finishing of natural or synthetic fibers, threads or textile fabrics. They give textile articles both the voluminous soft feel that is characteristic of silicone, as well as permanent elasticity and resilience.
Die erfindungsgemässen Silicon-Vinyl-Polymerisate besitzen ein gegenüber reinen Siliconen entsprechender Viskosität vergleichsweise günstigeres Emulgierverhalten.The silicone-vinyl polymers according to the invention have an emulsifying behavior which is comparatively more favorable than that of pure silicones of corresponding viscosity.
Sie lassen sich relativ leicht mit Hilfe der bekannten Emulgatoren und Emulgiertechniken in stabile Emulsionen überführen.They can be converted relatively easily into stable emulsions with the aid of the known emulsifiers and emulsification techniques.
Die verwendeten Emulgatoren bestehen zweckmässigerweise aus einer Mischung einer hydrophilen und einer hydrophoben Komponente. Geeignete Verbindungen sind z.B. Fettsäureester mehrwertiger Alkohole, wie z.B. Stearinsäureester von Glykolen, Glycerin oder Sorbit, sowie höhere Fettalkohole oder die Anlagerungsprodukte von Ethylenoxid an diese Fettalkohole, Fettsäuren oder ähnliche Verbindungen mit aktivem Wasserstoffatom. Geeignet sind aber auch anionaktive Emulgatoren wie Natriumlaurylsulfat oder Natriumdodecylbenzolsulfonat oder auch kationaktive Emulgatoren wie quaternäre Ammoniumverbindungen.The emulsifiers used expediently consist of a mixture of a hydrophilic and a hydrophobic component. Suitable compounds are, for example, fatty acid esters of polyhydric alcohols, such as stearic acid esters of glycols, glycerol or sorbitol, as well as higher fatty alcohols or the adducts of ethylene oxide with these fatty alcohols, fatty acids or similar compounds with an active hydrogen atom. However, anion-active emulsifiers such as sodium lauryl sulfate or sodium dodecylbenzenesulfonate or cation-active emulsifiers such as quaternary ammonium compounds are also suitable.
Die Aufbringung der erfindungsgemässen Silicon-Vinyl-Copolymere auf das zu behandelnde Substrat erfolgt nach den bekannten Methoden beispielsweise durch Foulardieren, Trocknen und Kondensieren, durch Sprühen oder Pflatschen.The silicone-vinyl copolymers according to the invention are applied to the substrate to be treated by the known methods, for example by padding, drying and condensing, by spraying or slapping.
Nach dem Auftragen der erfindungsgemässen wässrigen Siliconpfropfpolymerdispersion auf das textile Substrat, kann thermisch oder katalytisch eine Vernetzung der Siliconpfropfpolymerkomponente, gegebenenfalls unter Zusatz weiterer reaktiver Siliconderivate wie z.B. Polymethylhydrogensiloxanen erfolgen. Die rein thermische Vernetzung erfolgt bei Temperaturen ab etwa 120°C. Die katalytisch aktivierte Vernetzung kann bereits bei Raumtemperatur erfolgen. Als Katalysatoren kommen die bekannten Systeme wie Platin oder Platinverbindungen, Organozinnverbindungen aber auch Peroxide oder andere Radikalstarter in Frage. Mit Erfolg kann auch eine UV-Strahlen aktivierte Vernetzung durchgeführt werden. Durch die Vernetzung wird die Lösungsmittel- und Waschbeständigkeit der Ausrüstung verbessert. Bei der katalytischen Vernetzung empfiehlt es sich, entsprechende Inhibitoren, wie z.B. Acetylenalkohole, insbesondere Methylentinol, einzusetzen.After the aqueous silicone graft polymer dispersion according to the invention has been applied to the textile substrate, the silicone graft polymer component can be thermally or catalytically crosslinked, if appropriate with the addition of further reactive silicone derivatives such as e.g. Polymethylhydrogensiloxanen done. The purely thermal crosslinking takes place at temperatures from around 120 ° C. The catalytically activated crosslinking can take place at room temperature. Known systems such as platinum or platinum compounds, organotin compounds but also peroxides or other radical initiators are suitable as catalysts. UV-activated crosslinking can also be carried out successfully. Crosslinking improves the solvent and wash resistance of the equipment. In the case of catalytic crosslinking, it is advisable to use appropriate inhibitors, such as Use acetylene alcohols, especially methylenedinol.
Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie in ihrem Umfang einzuschränken.The following examples are intended to explain the invention in more detail without restricting its scope.
Wenn nichts anderes vermerkt, sind Mengenangaben als Gewichtsteile bzw. Gewichtsprozente zu verstehen.Unless otherwise noted, quantities are to be understood as parts by weight or percentages by weight.
Herstellung der Ausgangssubstanzen: Die Herstellung der Polydiorganosiloxane erfolgt in an sich bekannter Weise (vgl. W. Noll, «Chemie und Technologie der Silicone», Verlag Chemie, Weinheim/Bergstrasse, 2. Aufl., 1968, Kap. 5, S. 162 ff.).Preparation of the starting substances: The polydiorganosiloxanes are prepared in a manner known per se (cf. W. Noll, “Chemistry and Technology of Silicones”, Verlag Chemie, Weinheim / Bergstrasse, 2nd ed., 1968, chap. 5, p. 162 ff.).
Die in den Beispielen aufgeführten Siloxane sind wie folgt gekennzeichnet:
In einem 40 I-Autoklaven mit Rückflusskühler werden 10,5 kg eines Polysiloxans B, 9 kg eines Polysiloxans C vorgelegt und unter Stickstoffüberleitung auf 110°C erwärmt. Dann werden gleichzeitig 2 Lösungen innerhalb von 5 Stunden hinzugegeben:
Der Ansatz wird 1 Stunde nachgerührt und dann werden die flüchtigen Anteile destillativ entfernt.The mixture is stirred for 1 hour and then the volatile constituents are removed by distillation.
Viskosität bei 25°C: 12000 mPas.Viscosity at 25 ° C: 12000 mPas.
In einem 6 I-Rührkessel werden unter Schutzgas 3 kg Polysiloxan B, 150 g Polysiloxan C auf 100°C erwärmt. Dann wird eine Lösung aus
- 1,75 g kg n-Butylacrylat
- 15 g Tetrahydrobenzaldehydbenzylenolether 7,5 g t-Butylperpivalat
in 5 Stunden hinzugepumpt. Man rührt 1 Stunde nach und zieht die flüchtigen Anteile im Vakuum ab. Das Endprodukt hat bei 25°C eine Viskosität von 40 mPa - s und folgenden Zusammensetzung:
- 1.75 g kg of n-butyl acrylate
- 15 g of tetrahydrobenzaldehyde benzyl enol ether 7.5 g of t-butyl perpivalate
pumped in 5 hours. The mixture is stirred for 1 hour and the volatile constituents are stripped off in vacuo. The end product has a viscosity of 40 mPa - s at 25 ° C and the following composition:
In einem 6 I-Rührkessel werden unter Stickstoff 1500 g Polysiloxan B, 750 g Polysiloxan D, 750 g Polysiloxan C, 1 g Tetrahydrobenzaldehydenolether auf 150°C aufgeheizt. Dann werden zwei Lösungen gleichzeitig innerhalb von 4 Stunden hinzugegeben:
Der Ansatz wird 1 Stunde bei 150°C nachgerührt, sodann evakuiert und praktisch vollständig von nicht umgesetzten Monomeren befreit. Das erhaltene Pfropfpolymerisat weist eine Viskosität von 1500 mPas bei 25°C auf und weist eine Zusammensetzung auf, die einem 88%igen Monomerumsatz entspricht.The mixture is stirred at 150 ° C. for 1 hour, then evacuated and virtually completely freed of unreacted monomers. The graft polymer obtained has a viscosity of 1500 mPas at 25 ° C. and has a composition which corresponds to an 88% monomer conversion.
In einen 6 I-Rührkessel werden unter Stickstoff die unter Vorlage angegebenen Komponenten eingefüllt und auf 110°C erwärmt. Innerhalb von 3 Stunden wird die Monomer-Initiatorlösung hinzugegeben und dann 1 Stunde nachgerührt. Nach Abziehen der flüchtigen Anteile im Vakuum wird abgekühlt.
In einem 6 I-Stahlautoklaven werden 900 g Polysiloxan C und 600 g Polysiloxan B, 2,5 g di-tert.-Butylperoxid und 450 g Vinylidenfluorid vorgelegt. Der Ansatz wird auf 125°C erwärmt und 30 Minuten bei 125°C gerührt. Dann werden Lösung 1 und 2 innerhalb von 3 Stunden hinzugegeben.
Der Ansatz wird 1 Stunde bei 125°C nachgerührt, vorsichtig entspannt und evakuiert. Die flüchtigen Anteile werden abgezogen. Das Pfropfpolymerisat enthält
- 45 Gew.-% polymerisierte Einheiten aus Vinyli-. denfluorid
- 22 Gew.-% Einheiten aus Polysiloxan B
- 33 Gew.-% Einheiten aus Polysiloxan C
- 45% by weight polymerized vinyli units. the fluoride
- 22% by weight of polysiloxane B units
- 33% by weight units of polysiloxane C
Zu 40,0 kg Pfropfcopolymerisat des Beispiels 1 werden unter Rühren 1,4 kg eines mit 50 Mol Ethylenoxid umgesetzten Oleylalkohols und 1,2 kg eines mit 6 Mol Ethylenoxid umgesetzten Tridecylalkohols gegeben. Die Mischung wird auf 60°C erwärmt und unter Rühren werden 57,4 kg entionisiertes Wasser eingearbeitet. Man erhält eine homogene und stabile Emulsion des Pfropfcopolymers. Gegebenenfalls kann zur feineren Verteilung mittels einer Hochdruckhomogenisiermaschine (z.B. Alfa-Laval, Typ SH 20) in einem oder mehreren Gängen bei 200 bar homogenisiert werden.1.4 kg of an oleyl alcohol reacted with 50 mol of ethylene oxide and 1.2 kg of a tridecyl alcohol reacted with 6 mol of ethylene oxide are added to 40.0 kg of graft copolymer of Example 1 with stirring. The mixture is heated to 60 ° C. and 57.4 kg of deionized water are incorporated with stirring. A homogeneous and stable emulsion of the graft copolymer is obtained. If necessary, homogenization can be carried out in one or more gears at 200 bar for fine distribution using a high-pressure homogenizing machine (e.g. Alfa-Laval, type SH 20).
In gleicher Verfahrensweise, wie in Beispiel 4 und 7 erläutert, erhält man Emulsionen aus den Copolymerisaten in folgenden Zusammensetzungen:
Zum Vergleich werden Muster der Baumwoll-Hemdenpopeline mit dem erfindungsgemässen Pfropfcopolymerisat wie folgt ausgerüstet:
Die Applikation erfolgt in der wie vorher beschriebenen Weise.The application takes place in the manner described above.
Zur Verbesserung des «wash and wear»-Verhaltens von Baumwoll-Hemdenpopeline werden die Materialien mit Kunstharzen ausgerüstet, z. B. mit Dimethyldihydroxyethylenharnstoff (= DMDHEU). Hierdurch wird einerseits das Entknitterungsverhalten, trocken und nass, deutlich verbessert, zum anderen der Griff, die Reissfestigkeit, die Einreissfestigkeit, die Scheuerfestigkeit und die Vernähbarkeit verschlechtert. Um diese Nachteile zu kompensieren, werden Acrylatdispersionen und Weichmachungsmittel auf Basis von Fettsäureamiden und/oder Siliconen der Ausrüstungsflotte zugesetzt.To improve the “wash and wear” behavior of cotton shirt poplin, the materials are treated with synthetic resins, e.g. B. with dimethyldihydroxyethylene urea (= DMDHEU). On the one hand, this significantly reduces the wrinkling behavior, dry and wet improves, on the other hand, the grip, the tear resistance, the tear resistance, the abrasion resistance and the sewability deteriorate. In order to compensate for these disadvantages, acrylate dispersions and plasticizers based on fatty acid amides and / or silicones are added to the finishing liquor.
Die Applikation erfolgt durch Tauchen (Flottenaufnahme 70-100% vom Warengewicht), Abquetschen und anschliessendes Trocknen. Hieran schliesst sich ein Kalandrier- und Kondensationsschritt bei 140-160 °C während 4 bis 6 Minuten an.
Im Vergleich zum Beispiel 11 bleibt beim erfindungsgemässen Beispiel 15 auch nach 5 Wäschen bei 60°C der vorteilhafte Griff, Reissfestigkeit und Knitterwinkel praktisch unverändert erhalten, während Beispiel 11 nach 5 Wäschen unter gleichen Bedingungen deutliche Verschlechterungen im Griff (rauh, leer) und deutliche Verminderung von Reissfestigkeit und Knitterwinkel aufweist.In comparison to Example 11, the advantageous handle, tear resistance and crease angle remain practically unchanged in Example 15 according to the invention even after 5 washes at 60 ° C., while Example 11 after 5 washes under the same conditions shows significant deteriorations in the handle (rough, empty) and significant reduction of tear resistance and crease angle.
Eine in Längsrichtung strukturierte 100%ige Co-Rundwirkware (100 kg) wird auf einer Düsenfärbemaschine mit Reaktivfarbstoffen gefärbt, mehrmals heiss und kalt gespült und bei Kochtemperatur geseift; so dass alle unfixierten Farbstoffanteile entfernt sind.A 100% co-circular knitted fabric (100 kg) structured in the longitudinal direction is dyed with reactive dyes on a nozzle dyeing machine, rinsed hot and cold several times and soaped at cooking temperature; so that all unfixed dye components are removed.
Das letzte Spülbad verbleibt in der Maschine. Hierzu werden 2 kg des erfindungsgemässen Pfropfcopolymerisates des Beispiels 4 (entspricht 2% v.WG.) über ein Ansatzgefäss gegeben. Der pH-Wert der Spülflotte wurde vorher mit Essigsäure auf 6.0 eingestellt.The last rinsing bath remains in the machine. For this purpose, 2 kg of the graft copolymer according to the invention from Example 4 (corresponds to 2% of the total weight) are passed through a batch vessel. The pH of the rinsing liquor was previously adjusted to 6.0 with acetic acid.
Das Behandlungsbad wird bei laufender Ware mit je 1 °C/min. auf 35°C aufgeheizt. Nach Erreichen der Endtemperatur verbleibt die Ware 15 min. in der Ausrüstungsflotte.The treatment bath is at 1 ° C / min. heated to 35 ° C. After reaching the final temperature, the goods remain for 15 minutes. in the equipment fleet.
Danach wird die Flotte abgelassen, die Ware dem Färbeapparat entnommen und bei 125°C kontinuierlich getrocknet. Der Griff der behandelten Ware ist voll, weich und oberflächenglatt.The liquor is then drained off, the goods are removed from the dyeing apparatus and dried continuously at 125 ° C. The handle of the treated goods is full, soft and smooth.
Die Prüfung dient zur Ermittlung der Dehnung und des Rücksprungvermögens (Rückformvermögen) von textilen Flächengebilden unter bestimmter statischer Zugbelastung mit nachfolgender Entlastung.The test serves to determine the elongation and the resilience (resilience) of textile fabrics under certain static tensile loads with subsequent relief.
Aus den zu prüfenden textilen Flächengebilden werden in Kett- und Schussrichtung, bei Gewirken in Längs- und Querrichtung, je 3 streifenförmige Proben von 300 mm Länge und 50 mm Breite entnommen.3 strip-shaped samples 300 mm long and 50 mm wide are taken from the textile fabrics to be tested in the warp and weft directions, and in knitted fabrics in the longitudinal and transverse directions.
Die Proben werden in einer oberen feststehenden und einer unteren beweglichen Einspannklemme so eingespannt, dass je 50 mm an der oberen und unteren Klemme überstehen. Von der 200 mm Einspannlänge werden die mittleren 100 mm als Messstrecke gekennzeichnet.The samples are clamped in an upper fixed and a lower movable clamping clamp so that 50 mm protrude from the upper and lower clamp. Of the 200 mm clamping length, the middle 100 mm are identified as the measuring section.
An der unteren Einspannklemme wird ein Gewicht befestigt, das zusammen mit dem Gewicht der Klemme eine Prüfkraft von 25 N (2,5 Kp) ergibt.A weight is attached to the lower clamp, which together with the weight of the clamp results in a test force of 25 N (2.5 Kp).
Nach einer Einwirkzeit von 30 Minuten wird die Längung des Prüflings gemessen und aus der Längenänderung die statische Dehnung in % berechnet.After an exposure time of 30 minutes, the elongation of the test specimen is measured and the static elongation in% is calculated from the change in length.
Nach Abnahme des Gewichtes (mit der unteren Klemme) wird nach 30 Minuten erneut gemessen und aus der verbliebenen Längenänderung die bleibende Dehnung in % berechnet.
Claims (6)
the sum of components 1. A + B and 1. + 2. always being 100% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83100041T ATE24217T1 (en) | 1982-01-16 | 1983-01-05 | GRAFT-MODIFIED SILOXANE DISPERSIONS FOR FINISHING TEXTILE MATERIALS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3201205 | 1982-01-16 | ||
| DE19823201205 DE3201205A1 (en) | 1982-01-16 | 1982-01-16 | GRAFT MODIFIED SILOXANE DISPERSIONS FOR EQUIPMENT OF TEXTILE MATERIALS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0084772A2 EP0084772A2 (en) | 1983-08-03 |
| EP0084772A3 EP0084772A3 (en) | 1983-08-24 |
| EP0084772B1 true EP0084772B1 (en) | 1986-12-10 |
Family
ID=6153211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83100041A Expired EP0084772B1 (en) | 1982-01-16 | 1983-01-05 | Grafted siloxane dispersions for the finishing of textile materials |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4464506A (en) |
| EP (1) | EP0084772B1 (en) |
| JP (1) | JPS58126378A (en) |
| AT (1) | ATE24217T1 (en) |
| BR (1) | BR8300181A (en) |
| DE (2) | DE3201205A1 (en) |
| ES (1) | ES519008A0 (en) |
| FI (1) | FI75878C (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684670A (en) * | 1983-08-26 | 1987-08-04 | General Electric Company | Ultraviolet radiation-curable silicone release compositions |
| JPH01168971A (en) * | 1987-12-23 | 1989-07-04 | Nisshin Kagaku Kogyo Kk | Elastic processing agent for fiber and feeling-improving agent |
| JPH01168972A (en) * | 1987-12-25 | 1989-07-04 | Nisshin Kagaku Kogyo Kk | Elastic processing agent for fiber providing hydrophilic properties |
| JP2703603B2 (en) * | 1989-02-09 | 1998-01-26 | 日信化学工業株式会社 | Fiber treatment agent |
| JP3007121B2 (en) * | 1990-08-02 | 2000-02-07 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane-acrylate copolymer emulsion |
| JP2513101B2 (en) * | 1992-01-23 | 1996-07-03 | 信越化学工業株式会社 | Air bag coating composition and air bag |
| JP2960304B2 (en) * | 1993-06-30 | 1999-10-06 | 信越化学工業株式会社 | Water repellent for fiber |
| US5464801A (en) * | 1993-12-30 | 1995-11-07 | Dow Corning Corporation | Catalyst compositions comprising rhodium catalyst complexes |
| US5413724A (en) * | 1993-12-30 | 1995-05-09 | Dow Corning Corporation | Fiber treatment compositions and methods for the preparation thereof |
| DE59600007D1 (en) * | 1995-03-09 | 1997-08-07 | Wacker Chemie Gmbh | Binder for textile fabrics |
| DE19629585C2 (en) * | 1995-09-06 | 1998-12-10 | Heidenhain Gmbh Dr Johannes | Angle measuring device |
| US6375685B2 (en) * | 1997-05-13 | 2002-04-23 | The Procter & Gamble Company | Textile finishing process |
| DE69823051T2 (en) * | 1997-10-24 | 2005-03-17 | Daikin Industries, Ltd. | AQUEOUS RESIN DISPERSION COMPOSITION |
| ATE300597T1 (en) | 1998-09-30 | 2005-08-15 | Unilever Nv | TREATMENT OF TISSUES |
| DE60105845T2 (en) * | 2000-12-15 | 2005-02-10 | Unilever N.V. | TEXTILE WASH |
| US6616980B2 (en) | 2001-04-24 | 2003-09-09 | Crompton Corporation | Emulsion polymerized acrylated silicone copolymer for wrinkle reduction |
| WO2005012432A1 (en) * | 2003-07-25 | 2005-02-10 | Dow Corning Corporation | Silicone rubber composition |
| US7452957B2 (en) * | 2005-08-31 | 2008-11-18 | Kimberly-Clark Worldwide, Inc. | Hydrophilic silicone elastomers |
| US20100145001A1 (en) * | 2006-12-12 | 2010-06-10 | Unilever Plc | branched organic-inorganic polymers |
| JP7008432B2 (en) * | 2017-03-31 | 2022-01-25 | 信越化学工業株式会社 | Fiber to which silicone is fixed and its manufacturing method |
| WO2018180615A1 (en) | 2017-03-31 | 2018-10-04 | 信越化学工業株式会社 | Fiber treatment agent for electron beam fixing |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL125765C (en) * | 1963-11-29 | |||
| US3555109A (en) * | 1967-09-08 | 1971-01-12 | Stauffer Wacker Silicone Corp | In situ generation of unique particulate matter in organopolysiloxanes |
| US3627836A (en) * | 1968-11-15 | 1971-12-14 | Stauffer Wacker Silicone Corp | Modified organopolysiloxanes with mono and polyolefinic cross-linked particles generated in situ |
| BE754668A (en) * | 1969-08-13 | 1971-02-10 | Stauffer Wacker Silicone Corp | MODIFIED ORGANOPOLYSILOXANES AND THEIR PREPARATION |
| US4014851A (en) * | 1973-12-26 | 1977-03-29 | General Electric Company | Polyolefin-filled vinyloranopolysiloxane composition and method of preparation |
| US4123472A (en) * | 1975-09-05 | 1978-10-31 | Sws Silicones Corporation | Oil resistant modified silicone composition |
| DE2608894A1 (en) * | 1976-03-04 | 1977-09-08 | Pfersee Chem Fab | PROCESS FOR MANUFACTURING MODIFIED POLYMERIZES AND THEIR USE |
| US4070526A (en) * | 1976-05-20 | 1978-01-24 | Dow Corning Corporation | Radiation-curable coating compositions comprising mercaptoalkyl silicone and vinyl monomer, method of coating therewith and coated article |
| DE2641201A1 (en) * | 1976-09-14 | 1978-03-16 | Consortium Elektrochem Ind | MIXTURES CONTAINING DIORGANOPOLYSILOXANES AND PROCESS FOR THEIR PREPARATION |
| US4166078A (en) * | 1977-12-16 | 1979-08-28 | Sws Silicones Corporation | Modified organopolysiloxane compositions |
| US4172101A (en) * | 1978-04-14 | 1979-10-23 | Sws Silicones Corporation | Modified organopolysiloxane compositions |
-
1982
- 1982-01-16 DE DE19823201205 patent/DE3201205A1/en not_active Withdrawn
- 1982-12-30 US US06/454,829 patent/US4464506A/en not_active Expired - Fee Related
-
1983
- 1983-01-05 EP EP83100041A patent/EP0084772B1/en not_active Expired
- 1983-01-05 DE DE8383100041T patent/DE3368302D1/en not_active Expired
- 1983-01-05 AT AT83100041T patent/ATE24217T1/en not_active IP Right Cessation
- 1983-01-13 FI FI830122A patent/FI75878C/en not_active IP Right Cessation
- 1983-01-13 JP JP58002925A patent/JPS58126378A/en active Pending
- 1983-01-14 BR BR8300181A patent/BR8300181A/en unknown
- 1983-01-14 ES ES519008A patent/ES519008A0/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58126378A (en) | 1983-07-27 |
| FI830122A0 (en) | 1983-01-13 |
| FI830122L (en) | 1983-07-17 |
| FI75878C (en) | 1988-08-08 |
| US4464506A (en) | 1984-08-07 |
| BR8300181A (en) | 1983-10-11 |
| EP0084772A2 (en) | 1983-08-03 |
| EP0084772A3 (en) | 1983-08-24 |
| DE3368302D1 (en) | 1987-01-22 |
| ATE24217T1 (en) | 1986-12-15 |
| ES8402895A1 (en) | 1984-02-16 |
| FI75878B (en) | 1988-04-29 |
| DE3201205A1 (en) | 1983-07-28 |
| ES519008A0 (en) | 1984-02-16 |
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