EP0306935A2 - Process for impregnating organic fibres - Google Patents
Process for impregnating organic fibres Download PDFInfo
- Publication number
- EP0306935A2 EP0306935A2 EP88114668A EP88114668A EP0306935A2 EP 0306935 A2 EP0306935 A2 EP 0306935A2 EP 88114668 A EP88114668 A EP 88114668A EP 88114668 A EP88114668 A EP 88114668A EP 0306935 A2 EP0306935 A2 EP 0306935A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bonded
- sic
- radicals
- organopolysiloxane
- silicon
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 238000009833 condensation Methods 0.000 claims abstract description 13
- 230000005494 condensation Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims description 3
- -1 hydrocarbon radicals Chemical class 0.000 description 50
- 150000003254 radicals Chemical class 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 239000000839 emulsion Substances 0.000 description 19
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 18
- 229920000742 Cotton Polymers 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- 239000004744 fabric Substances 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 102000011782 Keratins Human genes 0.000 description 3
- 108010076876 Keratins Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052799 carbon Chemical group 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 2
- HNUALPPJLMYHDK-UHFFFAOYSA-N C[CH]C Chemical compound C[CH]C HNUALPPJLMYHDK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical group CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- WPNRZVONKRBZDU-UHFFFAOYSA-L [dodecanoyloxy(diethyl)stannyl] dodecanoate Chemical compound CC[Sn+2]CC.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O WPNRZVONKRBZDU-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 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
- 235000009120 camo Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
- 229910052725 zinc Chemical class 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- D06M15/37—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
- Y10T442/2803—Polymeric coating or impregnation from a silane or siloxane not specified as lubricant or water repellent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
- Y10T442/2877—Coated or impregnated polyvinyl alcohol fiber fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
- Y10T442/291—Coated or impregnated polyolefin fiber fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
- Y10T442/291—Coated or impregnated polyolefin fiber fabric
- Y10T442/2918—Polypropylene fiber fabric
Definitions
- the invention relates to a process for impregnating organic fibers with organopolysiloxane (1) which, in addition to diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contains at least two monovalent SiC-bonded radicals with basic nitrogen, characterized in that that at least some of the SiC-bound radicals with basic nitrogen consist of SiC-bound N-cyclohexylaminoalkyl radicals.
- US Pat. No. 4,089,701 and DE-OS 35 03 457 (corresponding to US Ser. No. 807007) contain, as SiC-bonded radicals with basic nitrogen, N-alkylaminoalkyl radicals or N- (aminoalkyl) aminoalkyl radicals no N-cycloalkylaminoalkyl radicals mentioned.
- all organic fibers in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles can be impregnated, which previously could also be impregnated with organosilicon compounds.
- fibers that can be impregnated by the process according to the invention are thus those made of keratin, in particular wool, polyvinyl alcohol, copolymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose and mixtures from at least two such fibers.
- the fibers can be of natural or synthetic origin.
- the textiles can be in the form of fabric or pieces of clothing or parts of clothing.
- the shrinkage due to felting can be prevented by impregnation by the process according to the invention, especially if the keratin has been pretreated, rinsed and neutralized.
- the diorganosiloxane units in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, are preferably those represented by the formula can be reproduced, where R is the same or different monovalent hydrocarbon radicals, R1 is hydrogen or carbon and hydrogen atom (s) and, if appropriate, an ether oxygen atom, radicals free of multiple bonds with 1 to 15 carbon atoms per radical and a is 0 or 1 is.
- radicals R preferably contain 1 to 18 carbon atoms per radical.
- radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radical, and butyl, octyl, tetradecyl and octadecyl radicals; aliphatic hydrocarbon radicals with at least one double bond, such as the vinyl, allyl and butadienyl radical; cycloaliphatic hydrocarbon radicals, such as the cyclohexyl radical; aromatic hydrocarbon radicals such as the phenyl radical and naphthyl radicals; Alkaryl groups such as tolyl groups; and aralkyl radicals, such as the benzyl radical.
- at least 80% of the number of SiC-bonded hydrocarbon residues in the organopolysiloxane (1) are preferably methyl residues.
- hydrocarbon radicals R insofar as they represent hydrocarbon radicals free of multiple bonds with a maximum of 15 carbon atoms per radical, also apply in full to the hydrocarbon radicals R 1, the methyl, ethyl and isopropyl radicals being preferred.
- a a preferred example of a radical R 1 composed of carbon and hydrogen atoms and an ether oxygen is the rest of the formula CH3O (CH2) 2-.
- the organopolysiloxanes (1) preferably contain at least 100 diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, per molecule.
- the SiC-bonded N-cyclohexylaminoalkyl radicals are present in monoorganosiloxane and / or diorganosiloxane and / or triorganosiloxane units, which are preferably represented by the formulas can be reproduced, where R, R1 and a have the meaning given above, R2 is the same or different, divalent hydrocarbon radicals and b is 0, 1 or 2.
- radical R 2 is that of the formula - (CH2) 3- particularly preferred.
- the SiC-bound N-cyclohexyl-3-aminopropyl radical is particularly preferred as the SiC-bound N-cyclohexylaminoalkyl radical.
- organopolysiloxane (1) which may contain condensable groups bonded directly to silicon, further monoorganosiloxane and / or diorganosiloxane and / or triorganosiloxane units which have a SiC-bonded radical with basic nitrogen cannot be excluded.
- They are preferably those of the formula wherein R, R1, R2, a and b have the meaning given above and R3 is hydrogen or the same or different alkyl or aminoalkyl or iminoalkyl radicals.
- alkyl radicals R3 are the methyl, ethyl, n-propyl and isopropyl radical as well as butyl, octyl, tetradecyl and octadecyl radicals.
- aminoalkyl radicals R3 are those of the formula H2N (CH2) 2- H2N (CH2) 2NH (CH2) 3- H2N (CH2) 3- (CH3) 2N (CH2) - H2N (CH2) 5- H (NHCH2CH2) 3- and n-C4H9NHCH2CH2NHCH2CH2-.
- the number of siloxane units with an SiC-bonded radical with basic nitrogen is preferably 0.4% to 6% of the number of diorganosiloxane units, in which the both SiC-bonded organic radicals are monovalent hydrocarbon radicals.
- a type of organopolysiloxane (1) can be used. However, a mixture of at least two different types of organopolysiloxane (1) can also be used.
- the organopolysiloxane (1) or a mixture of at least two different types of organopolysiloxane (1) has an average viscosity of preferably 100 to 10,000 mPa.s at 25 ° C, particularly preferably 1000 to 5000 mPa.s at 25 ° C.
- the organopolysiloxane contains (1) condensable groups bonded directly to silicon, it can, together with (2a) organopolysiloxane, which has at least 3 Si-bonded hydrogen atoms per molecule, and (3) optionally a catalyst for the condensation of bonds bonded directly to silicon , condensable groups are used.
- organopolysiloxane can also be used together with (2b) trialkoxy- or tetraalkoxysilane and (3) optionally catalyst for the condensation of condensable groups directly bonded to silicon.
- the organopolysiloxanes (1) can be prepared in a manner known per se for any of the organopolysiloxanes which contain monovalent SiC-bonded radicals containing basic nitrogen.
- organopolysiloxane (2a) with at least 3 Si-bonded hydrogen atoms per molecule which in connection with directly organopolysiloxane (1) having silicon-bonded groups capable of condensation can be used in the process according to the invention
- the silicon valences, which are saturated by hydrogen and siloxane oxygen atoms are preferably saturated by methyl, ethyl or phenyl radicals or a mixture of at least two such hydrocarbon radicals. It is further preferred that each silicon atom to which a hydrogen atom is bound also has one of the preferred hydrocarbon radicals mentioned above bound.
- Particularly preferred organopolysiloxanes (2a) with at least 3 Si-bonded hydrogen atoms per molecule are those of the formula (CH3) 3SiO (SiR 4th 2nd O) pSi (CH3) 3, wherein R4 is hydrogen or the methyl, ethyl or phenyl radical and p is an integer from 10 to 500, with the proviso that at most one hydrogen atom is bonded to a silicon atom and that the ratio of R 4th 2nd SiO units in which both R4 are hydrocarbon radicals to the units with Si-bonded hydrogen is 3: 1 to 1: 4.
- R4 also preferably denotes a methyl radical if it is not hydrogen.
- organopolysiloxane can also be used as organopolysiloxanes (2a) with at least 3 Si-bonded hydrogen atoms per molecule.
- the organopolysiloxane (2a) is preferably used in amounts of 0.01 to 0.20 parts by weight of Si-bonded hydrogen per 100 parts by weight of organopolysiloxane (1).
- the trialkoxy- or tetraalkoxysilanes (2b) which can be used in the process according to the invention in conjunction with organopolysilaxane (1) having groups capable of condensation directly bonded to silicon are preferably those of the formula RSi (OR1) 3 or Si (OR1) 4 or partial hydrolyzates of trialkoxy or tetraalkoxysilanes with up to 10 silicon atoms per partial hydrolyzate, where R and R1 have the meaning given above.
- Trialkoxy- or tetraalkoxysilane (2b) is preferably used in amounts of 1 to 20 parts by weight per 100 parts by weight of organopolysiloxane (1).
- any catalysts for the condensation of condensable groups directly bonded to silicon can be used in the process according to the invention which have hitherto been used to promote the condensation of condensable groups directly bonded to silicon Groups could be used.
- Such catalysts are, in particular, carboxylic acid salts of tin or zinc, it being possible for hydrocarbon radicals to be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoates, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- ethylhexyltin di-2-ethylhexoate, dibutyl or dioctyltin diacylates, the acylate groups each being derived from alkanoic acids having 3 to 16 carbon atoms per acid, in which at least two of the valences of the carbon atom bonded to the carboxyl group are saturated by at least two carbon atoms other than that of the carboxy group , and zinc octoate.
- tin such as di-n-butyltin dilaurate, tin octoates,
- catalysts (3) are alkoxy titanates, such as butyl titanates and triethanolamine titanate, and zirconium compounds.
- catalysts (3) The same or different molecules of this type of catalyst can also be used as catalysts (3).
- the catalyst (3) is preferably used in amounts of 1 to 10 parts by weight per 100 parts by weight of organopolysiloxane (1).
- further substances such as can conventionally be used to impregnate organic fibers, can optionally be used in the process according to the invention.
- examples of such other substances in the terminal units are each a Si-bonded hydroxyl group having dimethylpolysiloxanes with a viscosity of at most 10,000 mPa.s at 25 ° C, dimethylpolysiloxanes endblocked by trimethylsiloxy groups with a viscosity of at most 10,000 mPa.s at 25 ° C and, especially if the fibers to be impregnated consist at least in part of cellulose or cotton, so-called "crease-free finishes", such as dimethyldihydroxyethylene urea (DMDHEU) in a mixture with zinc nitrate or magnesium chloride.
- DMDHEU dimethyldihydroxyethylene urea
- the substances used in the process according to the invention can be applied to the fiber to be impregnated in undiluted form or in the form of solutions in organic solvent or in the form of aqueous emulsions. If aqueous emulsions are used, these emulsions can in addition to water, dispersants and the above-mentioned substances to be dispersed, contain thickeners, such as poly-N-vinylpyrrolidone.
- the substances used in the process according to the invention are preferably applied in the form of aqueous emulsions to the fibers to be impregnated. Nonionic and cationogenic emulsifiers are preferred as dispersants in these dispersions. These emulsions can be prepared in a manner known for the emulsification of organopolysiloxanes.
- the substances used in the process according to the invention can be applied to the fibers to be impregnated in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
- the substances used in the process according to the invention are preferably applied in amounts such that the weight gain of the fiber by these substances, minus any diluents which may be used, is 1 to 20 percent by weight, based on the weight of the fiber.
- the crosslinking of the organosilicon compounds used in the process according to the invention which occurs when components (2a) or (2b) and optionally (3) are used, takes place at room temperature. You can by heating to z. B. accelerated 50 ° to 180 ° C.
- An emulsion as described in Example 1 under b) is prepared with a dimethylpolysiloxane which has a Si-bonded hydroxyl group and has a viscosity of 1010 mPa.s at 25 ° C. in the terminal units.
- a white cotton fabric with a weight of 180 g / cm2 is immersed in an emulsion E1, E2, E3 and E4, each containing 30 g / l of the emulsion, the preparation of which is described in Examples 1, 2, 3 and 4 , and the rest contains water.
- a white cotton fabric with a weight of 180 g / cm 2 is immersed in an emulsion VE1, VE2, VE3 and VE4, each containing 30 g / l of the emulsion, the preparation of which is described in comparative experiments 1, 2, 3 and 4, respectively , and the rest contains water.
- the cotton fabrics are then squeezed to 74% liquid absorption.
- the cotton fabrics impregnated in this way are then heated to 150 ° C. for 10 minutes.
- the grip was rated equally well for the cotton fabrics impregnated with the emulsions E1, E2, E4, VE1 and VE2, but was rated better than for the cotton fabrics impregnated with the emulsions E3 and VE3 and much better rated as for the cotton fabric impregnated with the emulsion VE4.
- Table 2 Yellowing assessment white cotton fabric impregnated with emulsion E1 E2 E3 E4 VE1 VE2 VE3 VE4 without 1) Berger whiteness 76.1 76.3 76.5 76.8 74.7 74.5 71.5 76.6 76.5 1) non-impregnated white cotton fabric
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Abstract
Organische Fasern werden mit Organopolysiloxan (1), das zusätzlich zu Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, mindestens zwei einwertige SiC-gebundene Reste mit basischen Stickstoff enthält, imprägniert, wobei mindestens ein Teil der SiC-gebundenen Reste mit basischem Stickstoff aus SiC-gebundenen N-Cyclohexylaminoalkyl-Resten besteht. Die SiC-gebundenen N-Cyclohexylaminoalkyl-Reste liegen in Monoorganosiloxan- und/oder Diorgansiloxan- und/oder Triorganosiloxaneinheiten vor. Bevorzugt als SiC-gebundener N-Cyclohexylaminoalkyl-Rest ist der SiC-gebundene N-Cyclohexyl-3-aminopropyl-Rest. Das Organopolysiloxan (1) enthält gegebenenfalls direkt an Silicium gebundene, kondensationsfähige Gruppen. Organopolysiloxan (1), das direkt an Silicium gebundene, kondensationsfähige Gruppen enthält, kann zusammen mit Organopolysiloxan (2a), das mindestens 3 Si-gebundene Wasserstoffatome je Molekül aufweist, oder zusammen mit Trialkoxy- oder Tetraalkoxysilanen (2b) und gegebenenfalls zusammen mit Katalysator (3) für die Kondensation von direkt an Silicium gebundene, kondensationsfähige Gruppen eingesetzt werden.Organic fibers are impregnated with organopolysiloxane (1) which, in addition to diorganosiloxane units in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contains at least two monovalent SiC-bonded radicals with basic nitrogen, at least some of the SiC-bonded radicals with basic nitrogen consists of SiC-bonded N-cyclohexylaminoalkyl residues. The SiC-bonded N-cyclohexylaminoalkyl radicals are present in monoorganosiloxane and / or diorganosiloxane and / or triorganosiloxane units. Preferred as the SiC-bonded N-cyclohexylaminoalkyl radical is the SiC-bonded N-cyclohexyl-3-aminopropyl radical. The organopolysiloxane (1) optionally contains condensable groups bonded directly to silicon. Organopolysiloxane (1), which contains condensable groups bonded directly to silicon, can be used together with organopolysiloxane (2a), which has at least 3 Si-bonded hydrogen atoms per molecule, or together with trialkoxy or tetraalkoxysilanes (2b) and optionally together with catalyst ( 3) can be used for the condensation of groups which are bonded directly to silicon and are capable of condensation.
Description
Aus US 4 098 701, ausgegeben 4. Juli 1978, P. M. Burrill et al., Dow Corning Limited und DE-OS 35 03 457, offengelegt 7. August 1986, K. Huhn et al., Wacker Chemie GmbH (entsprechende US Ser. No. 807007) ist es bereits bekannt, organische Fasern mit direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisenden Organopolysiloxan, das zusätzlich zu Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, mindestens zwei einwertige SiC-gebundene Reste mit basischen Stickstoff enthält, Organopolysiloxan mit mindestens drei Si-gebundenen Wasserstoffatomen je Molekül und Katalysator für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen zu imprägnieren.From US 4,098,701, issued July 4, 1978, PM Burrill et al., Dow Corning Limited and DE-OS 35 03 457, published August 7, 1986, K. Huhn et al., Wacker Chemie GmbH (corresponding US Ser. No. 807007) it is already known to use organic fibers with organopolysiloxane having condensation groups directly bonded to silicon, in addition to diorganosiloxane units in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, at least two monovalent SiC-bonded radicals with basic nitrogen contains, to impregnate organopolysiloxane with at least three Si-bonded hydrogen atoms per molecule and catalyst for the condensation of condensable groups bonded directly to silicon.
Es ist Aufgabe der Erfindung, ein Verfahren zur Imprägnierung von organischen Fasern bereitzustellen, das den Fasern angenehmen Griff verleiht, und bei dem die Vergilbung der organischen Fasern besonders gering ist.It is an object of the invention to provide a method for impregnating organic fibers which gives the fibers a pleasant grip and in which the yellowing of the organic fibers is particularly low.
Gegenstand der Erfindung ist ein Verfahren zur Imprägnierung von organischen Fasern mit Organopolysiloxan (1) das zusätzlich zu Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, mindestens zwei einwertige SiC-gebundene Reste mit basischem Stickstoff enthält, dadurch gekennzeichnet, daß mindestens ein Teil der SiC-gebundenen Reste mit basischem Stickstoff aus SiC-gebundenen N-Cyclohexylaminoalkyl-Resten besteht.The invention relates to a process for impregnating organic fibers with organopolysiloxane (1) which, in addition to diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contains at least two monovalent SiC-bonded radicals with basic nitrogen, characterized in that that at least some of the SiC-bound radicals with basic nitrogen consist of SiC-bound N-cyclohexylaminoalkyl radicals.
In US 4 089 701 sowie in der DE-OS 35 03 457 (entsprechend US Ser. No. 807007) sind als SiC-gebundene Reste mit basischem Stickstoff N-Alkylaminoalkyl-Reste, bzw. N-(Aminoalkyl)aminoalkyl-Reste, aber keine N-Cycloalkylaminoalkyl-Reste genannt.US Pat. No. 4,089,701 and DE-OS 35 03 457 (corresponding to US Ser. No. 807007) contain, as SiC-bonded radicals with basic nitrogen, N-alkylaminoalkyl radicals or N- (aminoalkyl) aminoalkyl radicals no N-cycloalkylaminoalkyl radicals mentioned.
Nach dem erfindungsgemäßen Verfahren können alle organischen Fasern in Form von Fäden, Garnen, Vliesen, Matten, Strängen,gewebten, gewirkten oder gestrickten Textilien imprägniert werden, die auch bisher mit Organosiliciumverbindungen imprägniert werden konnten. Beispiele für Fasern, die nach dem erfindungsgemäßen Verfahren imprägniert werden können, sind somit solche aus Keratin, insbesondere Wolle, Polyvinylalkohol, Mischpolymere von Vinylacetat, Baumwolle, Rayon, Hanf, natürliche Seide, Polypropylen, Polyethylen, Polyester, Polyurethan, Polyamid, Cellulose und Gemische aus mindestens zwei solcher Fasern. Wie aus der vorstehenden Aufzählung ersichtlich, können die Fasern natürlicher oder synthetischer Herkunft sein. Die Textilien können in Form von Stoffbahnen oder Kleidungsstucken bzw. Teilen von Kleidungsstücken vorliegen.According to the method according to the invention, all organic fibers in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles can be impregnated, which previously could also be impregnated with organosilicon compounds. Examples of fibers that can be impregnated by the process according to the invention are thus those made of keratin, in particular wool, polyvinyl alcohol, copolymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose and mixtures from at least two such fibers. As can be seen from the above list, the fibers can be of natural or synthetic origin. The textiles can be in the form of fabric or pieces of clothing or parts of clothing.
Bei Keratin, insbesondere Wolle, kann durch Imprägnierung nach dem erfindungsgemäßen Verfahren, vor allem, wenn das Keratin mit Chlor vorbehandelt, gespült und neutralisiert wurde, das Schrumpfen durch Verfilzen verhindert werden.In the case of keratin, in particular wool, the shrinkage due to felting can be prevented by impregnation by the process according to the invention, especially if the keratin has been pretreated, rinsed and neutralized.
Im Organopolysiloxan (1), das gegebenenfalls direkt am Silicium gebundene, kondensationsfähige Gruppen enthält, sind die Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, vorzugsweise solche, die durch die Formel
Vorzugsweise enthälten die Reste R 1 bis 18 Kohlenstoffatom(e)je Rest. Beispiele für Reste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl- und Isopropylrest sowie Butyl-, Octyl-, Tetradecyl- und Octadecylreste; aliphatische Kohlenwasserstoffreste mit mindestens einer Doppelbindung, wie der Vinyl-, Allyl- und Butadienylrest; cycloaliphatische Kohlenwasserstoffreste, wie der Cyclohexylrest; aromatische Kohlenwasserstoffreste, wie der Phenylrest und Naphthylreste; Alkarylreste, wie Tolylreste; und Aralkylreste, wie der Benzylrest. Insbesondere wegen der leichteren Zugänglichkeit sind vorzugsweise mindestens 80 % der Anzahl der SiC-gebundenen Kohlenwasserstoffreste im Organopolysiloxan (1) Methylreste.The radicals R preferably contain 1 to 18 carbon atoms per radical. Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radical, and butyl, octyl, tetradecyl and octadecyl radicals; aliphatic hydrocarbon radicals with at least one double bond, such as the vinyl, allyl and butadienyl radical; cycloaliphatic hydrocarbon radicals, such as the cyclohexyl radical; aromatic hydrocarbon radicals such as the phenyl radical and naphthyl radicals; Alkaryl groups such as tolyl groups; and aralkyl radicals, such as the benzyl radical. In particular because of the easier accessibility, at least 80% of the number of SiC-bonded hydrocarbon residues in the organopolysiloxane (1) are preferably methyl residues.
Die Beispiele für Kohlenwasserstoffreste R, soweit sie von Mehrfachbindungen freie Kohlenwasserstoffreste mit höchstens 15 Kohlenstoffatomen je Rest darstellen, gelten im vollen Umfang auch für die Kohlenwasserstoffreste R¹, wobei die Methyl-, Ethyl- und Isopropylreste bevorzugt sind. Ein bevorzugtes Beispiel für einen aus Kohlenstoff- und Wasserstoffatomen sowie einem Ethersauerstoff aufgebauten Rest R¹ ist der Rest der Formel
CH₃O(CH₂)₂-.
Vorzugsweise enthalten die Organopolysiloxane (1) mindestens 100 Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, je Molekül.The examples of hydrocarbon radicals R, insofar as they represent hydrocarbon radicals free of multiple bonds with a maximum of 15 carbon atoms per radical, also apply in full to the hydrocarbon radicals R 1, the methyl, ethyl and isopropyl radicals being preferred. A a preferred example of a radical R 1 composed of carbon and hydrogen atoms and an ether oxygen is the rest of the formula
CH₃O (CH₂) ₂-.
The organopolysiloxanes (1) preferably contain at least 100 diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, per molecule.
Im Organopolysiloxan (1), das gegebenenfalls direkt an Silicium gebundene kondensationsfähige Gruppen enthält, liegen die SiC-gebunden N-Cyclohexylaminoalkyl-Reste in Monoorganosiloxan- und/oder Diorganosiloxan- und/oder Triorganosiloxaneinheiten vor, die vorzugsweise durch die Formeln
Insbesondere wegen der leichteren Zugänglichkeit ist als Rest R² derjenige der Formel
-(CH₂)₃-
besonders bevorzugt. Weitere Beispiele für Reste R² sind solche der Formel
-CH₂-
-(CH₂)₂-
-(CH₂)₄-
-C₆H₄- und
-CH₂CH = CHCH₂-.
In particular because of the easier accessibility, the radical R 2 is that of the formula
- (CH₂) ₃-
particularly preferred. Further examples of radicals R² are those of the formula
-CH₂-
- (CH₂) ₂-
- (CH₂) ₄-
-C₆H₄- and
-CH₂CH = CHCH₂-.
Besonders bevorzugt als SiC-gebundener N-Cyclohexylaminoalkyl-Rest ist der SiC-gebundene N-Cyclohexyl-3-aminopropyl-Rest.The SiC-bound N-cyclohexyl-3-aminopropyl radical is particularly preferred as the SiC-bound N-cyclohexylaminoalkyl radical.
Im Organopolysiloxan (1), das gegebenenfalls direkt an Silicium gebundene, kondensationsfähige Gruppen enthält, sind weitere Monoorganosiloxan- und/oder Diorganosiloxan- und/oder Triorganosiloxaneinheiten, die einen SiC-gebundenen Rest mit basischem Stickstoff aufweisen, nicht ausgeschlossen. Vorzugsweise sind es solche der Formel
Beispiele für Alkylreste R³ sind der Methyl-, Ethyl-, n-Propyl- und Isopropylrest sowie Butyl-, Octyl-, Tetradecyl- und Octadecylreste.Examples of alkyl radicals R³ are the methyl, ethyl, n-propyl and isopropyl radical as well as butyl, octyl, tetradecyl and octadecyl radicals.
Beispiele für Aminoalkylreste R³ sind solche der Formel
H₂N(CH₂)₂-
H₂N(CH₂)₂NH(CH₂)₃-
H₂N(CH₂)₃-
(CH₃)₂N(CH₂)-
H₂N(CH₂)₅-
H(NHCH₂CH₂)₃- und
n-C₄H₉NHCH₂CH₂NHCH₂CH₂-.
Examples of aminoalkyl radicals R³ are those of the formula
H₂N (CH₂) ₂-
H₂N (CH₂) ₂NH (CH₂) ₃-
H₂N (CH₂) ₃-
(CH₃) ₂N (CH₂) -
H₂N (CH₂) ₅-
H (NHCH₂CH₂) ₃- and
n-C₄H₉NHCH₂CH₂NHCH₂CH₂-.
Vorzugsweise beträgt die Anzahl der Siloxaneinheiten mit einem SiC-gebundenen Rest mit basischem Stickstoff 0,4 % bis 6 % der Anzahl der Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind.The number of siloxane units with an SiC-bonded radical with basic nitrogen is preferably 0.4% to 6% of the number of diorganosiloxane units, in which the both SiC-bonded organic radicals are monovalent hydrocarbon radicals.
Es kann eine Art von Organopolysiloxan (1) eingesetzt werden. Es kann aber auch ein Gemisch aus mindestens zwei verschiedenen Arten von Organopolysiloxan (1) eingesetzt werden.A type of organopolysiloxane (1) can be used. However, a mixture of at least two different types of organopolysiloxane (1) can also be used.
Das Organopolysiloxan (1) oder ein Gemisch aus mindestens zwei verschiedenen Arten von Organopolysiloxan (1) hat eine durchschnittliche Viskosität von vorzugsweise 100 bis 10 000 mPa.s bei 25°C, besonders bevorzugt 1000 bis 5000 mPa.s bei 25°C.The organopolysiloxane (1) or a mixture of at least two different types of organopolysiloxane (1) has an average viscosity of preferably 100 to 10,000 mPa.s at 25 ° C, particularly preferably 1000 to 5000 mPa.s at 25 ° C.
Enthält das Organopolysiloxan (1) direkt an Silicium gebundene, kondensationsfähige Gruppen, so kann es zusammen mit (2a) Organopolysiloxan, das mindestens 3 Si-gebundene Wasserstoffatome je Molekül aufweist, und (3) gegebenenfalls einem Katalysator für die Kondensation von direkt an Silicium gebundene, kondensationsfähige Gruppen eingesetzt werden. Ebenso kann solches Organopolysiloxan zusammen mit (2b) Trialkoxy- oder Tetraalkoxysilan und (3) gegebenenfalls Katalysator für die Kondensation von direkt an Silicium gebundene, kondensationsfähige Gruppen eingesetzt werden.If the organopolysiloxane contains (1) condensable groups bonded directly to silicon, it can, together with (2a) organopolysiloxane, which has at least 3 Si-bonded hydrogen atoms per molecule, and (3) optionally a catalyst for the condensation of bonds bonded directly to silicon , condensable groups are used. Such organopolysiloxane can also be used together with (2b) trialkoxy- or tetraalkoxysilane and (3) optionally catalyst for the condensation of condensable groups directly bonded to silicon.
Die Herstellung der Organopolysiloxane (1) kann in beliebiger für die Herstellung von Organopolysiloxanen, die einwertige SiC-gebundene Reste mit basischem Stickstoff enthalten, an sich bekannter Weise erfolgen.The organopolysiloxanes (1) can be prepared in a manner known per se for any of the organopolysiloxanes which contain monovalent SiC-bonded radicals containing basic nitrogen.
Im Organopolysiloxan (2a) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül, das in Verbindung mit direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendem Organopolysiloxan (1) bei dem erfindungsgemäßen Verfahren eingesetzt werden kann, sind die anders als durch Wasserstoff- und Siloxansauerstoffatome abgesättigten Siliciumvalenzen vorzugsweise durch Methyl-, Ethyl- oder Phenylreste oder ein Gemisch aus mindestens zwei solcher Kohlenwasserstoffreste abgesättigt. Weiterhin ist bevorzugt, daß an jedes Siliciumatom, an das ein Wasserstoffatom gebunden ist, auch einer der vorstehend genannten bevorzugten Kohlenwasserstoffreste gebunden ist.In organopolysiloxane (2a) with at least 3 Si-bonded hydrogen atoms per molecule, which in connection with directly organopolysiloxane (1) having silicon-bonded groups capable of condensation can be used in the process according to the invention, the silicon valences, which are saturated by hydrogen and siloxane oxygen atoms, are preferably saturated by methyl, ethyl or phenyl radicals or a mixture of at least two such hydrocarbon radicals. It is further preferred that each silicon atom to which a hydrogen atom is bound also has one of the preferred hydrocarbon radicals mentioned above bound.
Besonders bevorzugt als Organopolysiloxane (2a) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül sind solche der Formel
(CH₃)₃SiO(SiR
worin R⁴ Wasserstoff oder den Methyl-, Ethyl- oder Phenylrest und p eine ganze Zahl im Wert von 10 bis 500 bedeutet, mit der Maßgabe, daß an ein Siliciumatom höchstens ein Wasserstoffatom gebunden ist und daß das Verhältnis von R
(CH₃) ₃SiO (SiR
wherein R⁴ is hydrogen or the methyl, ethyl or phenyl radical and p is an integer from 10 to 500, with the proviso that at most one hydrogen atom is bonded to a silicon atom and that the ratio of R
Auch als Organopolysiloxane (2a) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül können gleiche oder verschiedene Moleküle dieser Organopolysiloxanart eingesetzt werden.The same or different molecules of this type of organopolysiloxane can also be used as organopolysiloxanes (2a) with at least 3 Si-bonded hydrogen atoms per molecule.
Vorzugsweise wird das Organopolysiloxan (2a) in Mengen von 0,01 bis 0,20 Gewichtsteilen Si-gebundenen Wasserstoffs je 100 Gewichtsteile Organopolysiloxan (1) eingesetzt.The organopolysiloxane (2a) is preferably used in amounts of 0.01 to 0.20 parts by weight of Si-bonded hydrogen per 100 parts by weight of organopolysiloxane (1).
Als Trialkoxy- oder Tetraalkoxysilane (2b), die in Verbindung mit direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendem Organopolysilaxan (1) bei dem erfindungsgemäßen Verfahren eingesetzt werden können, werden vorzugsweise solche der Formel
RSi(OR¹)₃ oder Si(OR¹)₄
oder Teilhydrolysate von Trialkoxy- oder Tetraalkoxysilanen mit bis zu 10 Siliciumatomen je Teilhydrolysat eingesetzt, wobei R und R¹ die oben dafür angegebene Bedeutung haben.The trialkoxy- or tetraalkoxysilanes (2b) which can be used in the process according to the invention in conjunction with organopolysilaxane (1) having groups capable of condensation directly bonded to silicon are preferably those of the formula
RSi (OR¹) ₃ or Si (OR¹) ₄
or partial hydrolyzates of trialkoxy or tetraalkoxysilanes with up to 10 silicon atoms per partial hydrolyzate, where R and R¹ have the meaning given above.
Vorzugsweise wird Trialkoxy- oder Tetraalkoxysilan (2b) in Mengen von 1 bis 20 Gewichtsteilen je 100 Gewichtsteile Organopolysiloxan (1) eingesetzt.Trialkoxy- or tetraalkoxysilane (2b) is preferably used in amounts of 1 to 20 parts by weight per 100 parts by weight of organopolysiloxane (1).
Als Katalysatoren (3) für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen können bei dem erfindungsgemäßen Verfahren beliebige Katalysatoren für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen eingesetzt werden, die bisher zur Förderung der Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen eingesetzt werden konnten. Beispiele für solche Katalysatoren sind insbesondere Carbonsäuresalze von Zinn oder Zink, wobei an Zinn Kohlenwasserstoffreste direkt gebunden sein können, wie Di-n-butylzinndilaurat, Zinnoctoate, Di-2-ethylzinndilaurat, Di-n-butylzinndi-2-ethylhexoat, Di-2-ethylhexylzinndi-2-ethylhexoat, Dibutyl- oder Dioctylzinndiacylate, wobei sich die Acylatgruppen jeweils von Alkansäuren mit 3 bis 16 Kohlenstoffatomen je Säure ableiten, bei denen mindestens zwei der Valenzen des an die Carboxylgruppe gebundenen Kohlenstoffatoms durch mindestens zwei andere Kohlenstoffatome als dasjenige der Carboxygruppe abgesättigt sind, und Zinkoctoate.As catalysts (3) for the condensation of condensable groups directly bonded to silicon, any catalysts for the condensation of condensable groups directly bonded to silicon can be used in the process according to the invention which have hitherto been used to promote the condensation of condensable groups directly bonded to silicon Groups could be used. Examples of such catalysts are, in particular, carboxylic acid salts of tin or zinc, it being possible for hydrocarbon radicals to be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoates, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- ethylhexyltin di-2-ethylhexoate, dibutyl or dioctyltin diacylates, the acylate groups each being derived from alkanoic acids having 3 to 16 carbon atoms per acid, in which at least two of the valences of the carbon atom bonded to the carboxyl group are saturated by at least two carbon atoms other than that of the carboxy group , and zinc octoate.
Weitere Beispiele für Katalysatoren (3) sind Alkoxytitanate, wie Butyltitanate und Triethanolamintitanat, sowie Zirkoniumverbindungen.Further examples of catalysts (3) are alkoxy titanates, such as butyl titanates and triethanolamine titanate, and zirconium compounds.
Auch als Katalysatoren (3) können gleiche oder verschiedene Moleküle dieser Katalysatorart eingesetzt werden.The same or different molecules of this type of catalyst can also be used as catalysts (3).
Vorzugsweise wird der Katalysator (3) in Mengen von 1 bis 10 Gewichtsteilen je 100 Gewichtsteile Organopolysiloxan (1) eingesetzt.The catalyst (3) is preferably used in amounts of 1 to 10 parts by weight per 100 parts by weight of organopolysiloxane (1).
Zusätzlich zu den bisher genannten Stoffen (1), (2a), (2b), und (3) können bei dem erfindungsgemäßen Verfahren gegebenenfalls weitere Stoffe, wie sie zur Imprägnierung von organischen Fasern herkömmlicherweise mitverwendet werden können, mitverwendet werden. Beispiele für derartige weitere Stoffe sind in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisende Dimethylpolysiloxane mit einer Viskosität von höchstens 10 000 mPa.s bei 25°C, durch Trimethylsiloxygruppen endblockerte Dimethylpolysiloxane mit einer Viskisität von höchstens 10 000 mPa.s bei 25°C und, vor allem, wenn die zu imprägnierenden Fasern mindestens zum Teil aus Cellulose oder Baumwolle bestehen, sogenannte "Knitterfrei-Ausrüstungen", wie Dimethyldihydroxyethylenharnstoff (DMDHEU) im Gemisch mit Zinknitrat oder Magnesiumchlorid.In addition to the previously mentioned substances (1), (2a), (2b), and (3), further substances, such as can conventionally be used to impregnate organic fibers, can optionally be used in the process according to the invention. Examples of such other substances in the terminal units are each a Si-bonded hydroxyl group having dimethylpolysiloxanes with a viscosity of at most 10,000 mPa.s at 25 ° C, dimethylpolysiloxanes endblocked by trimethylsiloxy groups with a viscosity of at most 10,000 mPa.s at 25 ° C and, especially if the fibers to be impregnated consist at least in part of cellulose or cotton, so-called "crease-free finishes", such as dimethyldihydroxyethylene urea (DMDHEU) in a mixture with zinc nitrate or magnesium chloride.
Die bei dem erfindungsgemäßen Verfahren eingesetzten Stoffe können in unverdünnter Form oder in Form von Lösungen in organischem Lösungsmittel oder in Form wäßriger Emulsionen auf die zu imprägnierende Faser aufgetragen werden. Werden dabei wäßrige Emulsionen eingesetzt, so können diese Emulsionen zusätzlich zu Wasser, Dispergiermittel und den oben genannten, zu dispergierenden Stoffen Verdickungsmittel, wie Poly-N-vinylpyrrolidon, enthalten. Vorzugsweise werden die bei dem erfindungsgemäßen Verfahren eingesetzten Stoffe in Form wäßriger Emulsionen auf die zu imprägnierenden Fasern aufgetragen. Als Dispergiermittel in diesen Dispersionen sind nichtionogene und kationogene Emulgatoren bevorzugt. Die Herstellung dieser Emulsionen kann in für die Emulgierung von Organopolysiloxanen bekannter Weise erfolgen.The substances used in the process according to the invention can be applied to the fiber to be impregnated in undiluted form or in the form of solutions in organic solvent or in the form of aqueous emulsions. If aqueous emulsions are used, these emulsions can in addition to water, dispersants and the above-mentioned substances to be dispersed, contain thickeners, such as poly-N-vinylpyrrolidone. The substances used in the process according to the invention are preferably applied in the form of aqueous emulsions to the fibers to be impregnated. Nonionic and cationogenic emulsifiers are preferred as dispersants in these dispersions. These emulsions can be prepared in a manner known for the emulsification of organopolysiloxanes.
Das Auftragen der bei dem erfindungsgemäßen Verfahren verwendeten Stoffe auf die zu imprägnierenden Fasern kann in beliebiger für die Imprägnierung von Fasern geeigneter und vielfach bekannter Weise erfolgen, z. B. durch Tauchen, Streichen, Gießen, Sprühen, einschließlich Sprühen aus Aerosolverpackung, Aufwalzen, Klotzen oder Drucken.The substances used in the process according to the invention can be applied to the fibers to be impregnated in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
Vorzugsweise werden die bei dem erfingungsgemäßen Verfahren verwendeten Stoffe in solchen Mengen aufgetragen, daß die Gewichtszunahme der Faser durch diese Stoffe, abzüglich der dabei gegebenenfalls mitverwendeten Verdünnungsmittel, 1 bis 20 Gewichtsprozent, bezogen auf das Gewicht der Faser, beträgt.The substances used in the process according to the invention are preferably applied in amounts such that the weight gain of the fiber by these substances, minus any diluents which may be used, is 1 to 20 percent by weight, based on the weight of the fiber.
Die bei Mitverwendung der Bestandteile (2a) bzw. (2b) und ggf. (3) eintretende Vernetzung der bei dem erfindungsgemäßen Verfahren eingesetzten Organosiliciumverbindungen auf der Faser erfolgt bei Raumtemperatur. Sie kann durch Erwärmen auf z. B. 50° bis 180°C beschleunigt werden.The crosslinking of the organosilicon compounds used in the process according to the invention, which occurs when components (2a) or (2b) and optionally (3) are used, takes place at room temperature. You can by heating to z. B. accelerated 50 ° to 180 ° C.
In den folgenden Teilen der Beschreibung beziehen sich alle Angaben von Teilen und Prozentsätzen auf das Gewicht, soweit nichts anderes angegeben ist.In the following parts of the description, all parts and percentages are by weight unless otherwise stated.
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a) Ein Gemisch aus 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
und 150 Teilen einer Mischung von cyclischen Dimethylpolysiloxanen mit 3 bis 10 Siloxaneinheiten je Molekül und 0,03 Teilen einer 40-%-igen Lösung von Benzyltrimethylammoniumhydroxid in Methanol wird unter Stickstoff und Rühren 4 Stunden auf 80°C erwärmt. Dann wird das quarternäre Ammoniumhydroxid durch 60 Minuten Erwärmen auf 150°C bei 13 hPa (abs.) unwirksam gemacht und gleichzeitig das Organopolysiloxan von unter diesen Bedingungen siedende Bestandteilen befreit. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-Cyclohexyl-3-aminopropyl-Rest. Es hat eine Viskosität von 1200 mPa.s bei 25°C und eine Aminzahl (= Anzahl der ml 1-n-HCl, die zum Neutralisieren von 1g Substanz erforderlich sind) von 0,15.a) A mixture of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
and 150 parts of a mixture of cyclic dimethylpolysiloxanes with 3 to 10 siloxane units per molecule and 0.03 part of a 40% strength solution of benzyltrimethylammonium hydroxide in methanol are heated at 80 ° C. for 4 hours under nitrogen and with stirring. Then the quaternary ammonium hydroxide is rendered ineffective by heating for 60 minutes at 150 ° C. at 13 hPa (abs.) And at the same time the organopolysiloxane is freed from components boiling under these conditions. The organopolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N-cyclohexyl-3-aminopropyl radical. It has a viscosity of 1200 mPa.s at 25 ° C and an amine number (= number of ml 1-n-HCl required to neutralize 1 g substance) of 0.15. - b) 35 Teile des Organopolysiloxans, dessen Herstellung vorstehend unter a) beschrieben wurde, werden unter Verwendung von 4 Teilen Polyglykolether, der durch Umsetzung von Tributylphenol (1 Mol) mit Ethylenoxyd (13 Mol) hergestellt wurde, als Dispergiermittel in 61 Teilen Wasser emulgiert.b) 35 parts of the organopolysiloxane, the preparation of which was described above under a), are emulsified in 4 parts of water using 4 parts of polyglycol ether, which was prepared by reacting tributylphenol (1 mol) with ethylene oxide (13 mol), as the dispersant.
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a) Die in Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
9 Teile dieses Silans verwendet werden. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-Cyclohexyl-3-aminopropyl-Rest. Es hat eine Viskosität 1150 mPa.s bei 25°C und eine Aminzahl von 0,29.a) The procedure described in Example 1 under a) is repeated with the modification that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
9 parts of this silane can be used. The organopolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N-cyclohexyl-3-aminopropyl radical. It has a viscosity of 1150 mPa.s at 25 ° C and an amine number of 0.29. - b) Mit dem Organopolysiloxan, dessen Herstellung vorstehend unter a) beschrieben wurde, wird eine Emulsion wie im Beispiel 1 unter b) beschrieben, hergestellt.b) With the organopolysiloxane, the preparation of which was described above under a), an emulsion is produced as described in example 1 under b).
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a) Die in Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit den Abänderungen, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
10 Teile dieses Silans und anstelle von 150 Teilen der Mischung von cyclischen Dimethylpolysiloxanen mit 3 bis 10 Siloxaneinheiten je Molekül 90 Teile dieser Mischung von cyclischen Dimethylpolysiloxanen verwendet werden. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-Cyclohexylaminopropyl-Rest. Es hat eine Viskosität von 830 mPa.s bei 25°C und eine Aminzahl von 0,62.a) The procedure described in Example 1 under a) is repeated with the modifications that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
10 parts of this silane and 90 parts of this mixture of cyclic dimethylpolysiloxanes can be used instead of 150 parts of the mixture of cyclic dimethylpolysiloxanes with 3 to 10 siloxane units per molecule. The organopolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N-cyclohexylaminopropyl radical. It has a viscosity of 830 mPa.s at 25 ° C and an amine number of 0.62. - b) 35 Teile des Organopolysiloxans, dessen Herstellung vorstehend unter a) beschrieben wurde, wird unter Verwendung von 6 Teilen Polyglykolether, der durch Umsetzung von Tributylphenol (1 Mol) mit Ethylenoxid (8 Mol) hergestellt wurde, als Dispergiermittel in 61 Teilen Wasser emulgiert.b) 35 parts of the organopolysiloxane, the production of which was described above under a), is used of 6 parts of polyglycol ether, which was prepared by reacting tributylphenol (1 mol) with ethylene oxide (8 mol), as a dispersant in 61 parts of water.
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a) Die in Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
4,7 Teile des Silans der Formel
C₆H₁₁NH(CH₂)₃Si(OCH₃)₃
verwendet werden. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Monoorganosiloxaneinheiten mit einem SiC-gebundenen N-Cyclohexyl-3-aminopropyl-Rest. Es hat eine Viskosität von 1220 mPa.s bei 25°C und eine Aminzahl von 0,14.a) The procedure described in Example 1 under a) is repeated with the modification that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
4.7 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃Si (OCH₃) ₃
be used. The organopolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, monoorganosiloxane units with an SiC-bonded N-cyclohexyl-3-aminopropyl radical. It has a viscosity of 1220 mPa.s at 25 ° C and an amine number of 0.14. - b) Mit dem Organopolysiloxan, dessen Herstellung vorstehend unter a) beschrieben wurde, wird eine Emulsion wie im Beispiel 1 unter b) beschrieben, hergestellt.b) With the organopolysiloxane, the preparation of which was described above under a), an emulsion is produced as described in example 1 under b).
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a) Die in Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
2 Teile des Silans der Formel
NH₂(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂
verwendet werden. Das so erhaltene Organpolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-(2-Aminoethyl)-3-aminopropyl-Rest. Es hat eine Viskosität von 1050 m Pa.s bei 25°C und eine Aminzahl von 0,14.a) The procedure described in Example 1 under a) is repeated with the modification that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
2 parts of the silane of the formula
NH₂ (CH₂) ₂NH (CH₂) ₃SiCH₃ (OCH₃) ₂
be used. The organpolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N- (2-aminoethyl) -3-aminopropyl radical. It has a viscosity of 1050 m Pa.s at 25 ° C and an amine number of 0.14. - b) Mit dem Organopolysiloxan, dessen Herstellung vorstehend unter a) beschrieben wurde, wird eine Emulsion, wie im Beispiel 1 unter b) beschrieben, hergestellt.b) With the organopolysiloxane, the preparation of which was described above under a), an emulsion is produced as described in example 1 under b).
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a) Die im Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
4,3 Teile des Silans der Formel
NH₂(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂
verwendet wird. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationfähige gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-(2-Aminoethyl)-3-aminopropyl-Rest. Es hat eine Viskosität von 1020 mPa.s bei 25°C und eine Aminzahl von 0,27.a) The procedure described in Example 1 under a) is repeated with the modification that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
4.3 parts of the silane of the formula
NH₂ (CH₂) ₂NH (CH₂) ₃SiCH₃ (OCH₃) ₂
is used. The organopolysiloxane obtained in this way contains methoxy groups which are directly bondable to silicon and condensable groups and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N- (2-aminoethyl) -3-aminopropyl radical. It has a viscosity of 1020 mPa.s at 25 ° C and an amine number of 0.27. - b) Mit dem Organopolysiloxan, dessen Herstellung vorstehend unter a) beschrieben wurde, wird eine Emulsion wie im Beispiel 1 unter b) beschrieben, hergestellt.b) With the organopolysiloxane, the preparation of which was described above under a), an emulsion is produced as described in example 1 under b).
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a) Die im Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit den Abänderungen, daß anstelle von 4,5 Teilen des Silans der Formel
C₆H₁₁NH(CH₂)₃SiCH₃(OCH₃)₂
4,8 Teile des Silans der Formel
NH₂(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂
und anstelle von 150 Teilen der Mischung von cyclischen Dimethylpolysiloxan mit 3 bis 10 Siloxaneinheiten je Molekül 100 Teile dieser Mischung von cyclischen Dimethylpolysiloxanen verwendet werden. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten Diorganosiloxaneinheiten mit einem SiC-gebundenen N-(2-Aminoethyl)-3-aminopropyl-Rest. Es hat eine Viskosität von 960 m Pa.s bei 25°C und eine Aminzahl von 0,60.a) The procedure described in Example 1 under a) is repeated with the modifications that instead of 4.5 parts of the silane of the formula
C₆H₁₁NH (CH₂) ₃SiCH₃ (OCH₃) ₂
4.8 parts of the silane of the formula
NH₂ (CH₂) ₂NH (CH₂) ₃SiCH₃ (OCH₃) ₂
and instead of 150 parts of the mixture of cyclic dimethylpolysiloxane with 3 to 10 siloxane units per molecule, 100 parts of this mixture of cyclic dimethylpolysiloxanes can be used. The organopolysiloxane thus obtained contains, as condensable groups directly bonded to silicon, methoxy groups and, in addition to dimethylsiloxane units, diorganosiloxane units with an SiC-bonded N- (2-aminoethyl) -3-aminopropyl radical. It has a viscosity of 960 m Pa.s at 25 ° C and an amine number of 0.60. - b) Mit dem Organopolysiloxan, dessen Herstellung vorstehend unter a) beschrieben wurde, wird eine Emulsion, wie im Beispiel 1 unter b) beschrieben, hergestellt.b) With the organopolysiloxane, the preparation of which was described above under a), an emulsion is produced as described in example 1 under b).
Mit einem in den endständigen Einheiten je eine Si-gebundenen Hydroxylgruppe aufweisenden Dimethylpolysiloxan, das eine Viskosität von 1010 mPa.s bei 25°C besitzt, wird eine Emulsion, wie im Beispiel 1 unter b) beschrieben, hergestellt.An emulsion as described in Example 1 under b) is prepared with a dimethylpolysiloxane which has a Si-bonded hydroxyl group and has a viscosity of 1010 mPa.s at 25 ° C. in the terminal units.
Je ein weißes Baumwollgewebe mit einem Gewicht von 180g/cm² wird jeweils in eine Emulsion E1, E2, E3 bzw. E4 getaucht, die jeweils 30 g/l der Emulsion, deren Herstellung in den Beispielen 1, 2, 3 bzw. 4 beschrieben ist, und als Rest Wasser enthält. Ebenso wird je ein weißes Baumwollgewebe mit einem Gewicht von 180g/cm² jeweils in eine Emulsions VE1 VE2, VE3 bzw. VE4 getaucht, die jeweils 30 g/l der Emulsion, deren Herstellung in den Vergleichsversuchen 1, 2, 3 bzw. 4 beschrieben ist, und als Rest Wasser enthält. Die Baumwollgewebe werden dann jeweils auf 74 % Flüssigkeitsaufnahme abgequetscht. Die so imprägnierten Baumwollgewebe werden anschließend 10 Minuten auf 150°C erwärmt.A white cotton fabric with a weight of 180 g / cm² is immersed in an emulsion E1, E2, E3 and E4, each containing 30 g / l of the emulsion, the preparation of which is described in Examples 1, 2, 3 and 4 , and the rest contains water. Likewise, a white cotton fabric with a weight of 180 g / cm 2 is immersed in an emulsion VE1, VE2, VE3 and VE4, each containing 30 g / l of the emulsion, the preparation of which is described in comparative experiments 1, 2, 3 and 4, respectively , and the rest contains water. The cotton fabrics are then squeezed to 74% liquid absorption. The cotton fabrics impregnated in this way are then heated to 150 ° C. for 10 minutes.
Bei den so erhaltenen imprägnierten Baumwollgeweben wird der Griff und die Vergilbung bewertet (vgl. Tabelle 1 und 2).The grip and yellowing of the impregnated cotton fabrics thus obtained are evaluated (cf. Tables 1 and 2).
E1= E2= E4= VE1= VE2> E3= VE3»VE4
E1 = E2 = E4 = VE1 = VE2> E3 = VE3 »VE4
Der Griff wurde für die mit den Emulsionen E1, E2, E4, VE1 und VE2 imprägnierten Baumwollgewebe gleich gut bewertet, wurde aber besser bewertet als für die mit den Emulsionen E3 und VE3 imprägnierten Baumwollgewebe und sehr viel besser bewertet als für das mit der Emulsion VE4 imprägnierte Baumwollgewebe.
Die Bestimmung des Weißgrades ist in A. Berger, Die Farbe, Band 8, 1959, Seite 187-202 beschrieben. Für das nicht imprägnierte, weiße Baumwollgewebe wurde ein Wert von 76,5 ermittelt. Niedrigere Werte als 76,5 kennzeichnen eine Vergilbung des Gewebes, höhere Werte ein weißeres Gewebe.The determination of the degree of whiteness is described in A. Berger, Die Farbe, Volume 8, 1959, page 187-202. A value of 76.5 was determined for the non-impregnated, white cotton fabric. Lower values than 76.5 indicate yellowing of the tissue, higher values a whiter tissue.
Claims (7)
dadurch gekennzeichnet , daß die SiC-gebundenen N-Cyclohexylaminoalkyl-Reste in Monoorganosiloxan- und/oder Diorganosiloxan- und/oder Triorganosiloxaneinheiten vorliegen.2. The method according to claim 1,
characterized in that the SiC-bonded N-cyclohexylaminoalkyl radicals are present in monoorganosiloxane and / or diorganosiloxane and / or triorganosiloxane units.
dadurch gekennzeichnet, daß der SiC-gebundene N-Cyclohexylaminoalkyl-Rest ein SiC-gebundener N-Cyclohexyl-3-aminopropyl-Rest ist.3. The method according to claim 1 or 2,
characterized in that the SiC-bonded N-cyclohexylaminoalkyl radical is an SiC-bonded N-cyclohexyl-3-aminopropyl radical.
dadurch gekennzeichnet, daß das Organopolysiloxan (1) gemäß Anspruch 1, 2 oder 3 direkt an Silicium gebundene, kondensationsfähige Gruppen enthält.4. The method according to claim 1, 2 or 3,
characterized in that the organopolysiloxane (1) according to claim 1, 2 or 3 contains condensable groups bonded directly to silicon.
dadurch gekennzeichnet, daß direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendes Organopolysiloxan (1) gemäß Anspurch 1,2 oder 3 zusammen mit Organopolysiloxan (2a) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül eingesetzt wird.5. The method according to claim 1, 2 or 3,
characterized in that organopolysiloxane (1) bonded directly to silicon and having groups capable of condensation is used according to Claim 1, 2 or 3 together with organopolysiloxane (2a) with at least 3 Si-bonded hydrogen atoms per molecule.
dadurch gekennzeichnet, daß direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendes Organopolysiloxan (1) gemäß Anspruch 1,2 oder 3 zusammen mit Trialkoxy- oder Tetraalkoxysilan (2b) eingesetzt wird.6. The method according to claim 1, 2 or 3,
characterized in that organopolysiloxane (1) according to claim 1, 2 or 3 which is bonded directly to silicon and has condensable groups is used together with trialkoxy- or tetraalkoxysilane (2b).
dadurch gekennzeichnet, daß Katalysator (3) für die Kondensation von direkt an Silicium gebundene, kondensationsfähige Gruppen mitverwendet wird.7. The method according to claim 5 or 6,
characterized in that catalyst (3) is also used for the condensation of condensable groups bonded directly to silicon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88114668T ATE78531T1 (en) | 1987-09-10 | 1988-09-08 | PROCESS FOR IMPREGNATION OF ORGANIC FIBERS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3730413 | 1987-09-10 | ||
DE19873730413 DE3730413A1 (en) | 1987-09-10 | 1987-09-10 | METHOD FOR IMPREGNATING ORGANIC FIBERS |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0306935A2 true EP0306935A2 (en) | 1989-03-15 |
EP0306935A3 EP0306935A3 (en) | 1989-12-27 |
EP0306935B1 EP0306935B1 (en) | 1992-07-22 |
Family
ID=6335714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88114668A Expired - Lifetime EP0306935B1 (en) | 1987-09-10 | 1988-09-08 | Process for impregnating organic fibres |
Country Status (7)
Country | Link |
---|---|
US (1) | US4874662A (en) |
EP (1) | EP0306935B1 (en) |
JP (1) | JPH0197279A (en) |
KR (1) | KR950003854B1 (en) |
AT (1) | ATE78531T1 (en) |
AU (1) | AU609875B2 (en) |
DE (2) | DE3730413A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350604A2 (en) * | 1988-05-26 | 1990-01-17 | Toray Silicone Company, Limited | Fibre-treatment composition |
EP0651089A1 (en) * | 1993-10-27 | 1995-05-03 | Dow Corning Toray Silicone Company, Limited | Adsorption treatment method of fibers |
EP0692567A1 (en) * | 1994-07-14 | 1996-01-17 | Wacker-Chemie GmbH | Amionofunctional organopolysiloxane |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9002715D0 (en) * | 1990-02-07 | 1990-04-04 | Dow Corning | Method of treating fibrous materials |
US5182173A (en) * | 1990-05-07 | 1993-01-26 | Rogers Corporation | Coated particles and method for making same |
US5292575A (en) * | 1990-08-21 | 1994-03-08 | Aerospatiale Societe Nationale Industrielle | Sheet material for constructing high performance thermal screens |
DE4117864A1 (en) * | 1991-05-31 | 1992-12-03 | Pfersee Chem Fab | WAITER DISPERSIONS OF POLYSILOXANES |
DE4132647A1 (en) * | 1991-10-01 | 1993-04-08 | Pfersee Chem Fab | AQUEOUS DISPERSIONS OF NITROGEN POLYSILOXANS |
DE4133358A1 (en) * | 1991-10-09 | 1993-04-15 | Pfersee Chem Fab | AQUEOUS COMPOSITIONS WITH NITROGEN POLYSILOXANES |
DE4318794A1 (en) * | 1993-06-07 | 1994-12-08 | Pfersee Chem Fab | Organopolysiloxanes containing substituted 1,3.5-triazine units |
US6712121B2 (en) | 2001-10-12 | 2004-03-30 | Kimberly-Clark Worldwide, Inc. | Antimicrobially-treated fabrics |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4098701A (en) * | 1976-06-26 | 1978-07-04 | Dow Corning Limited | Process for treating fibres |
DE3503457A1 (en) * | 1985-02-01 | 1986-08-07 | Wacker-Chemie GmbH, 8000 München | METHOD FOR IMPREGNATING ORGANIC FIBERS |
US4639321A (en) * | 1985-01-22 | 1987-01-27 | The Procter And Gamble Company | Liquid detergent compositions containing organo-functional polysiloxanes |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5229207B2 (en) * | 1973-05-10 | 1977-08-01 | ||
JPS5638609A (en) * | 1979-09-05 | 1981-04-13 | Toshiba Corp | Monitoring method for plant |
US4247592A (en) * | 1980-03-12 | 1981-01-27 | Dow Corning Corporation | Method for treating synthetic textiles with aminoalkyl-containing polydiorganosiloxanes |
JPS5952403B2 (en) * | 1983-07-11 | 1984-12-19 | 旭光学工業株式会社 | Zoom lens barrel capable of macro photography |
DE3343575A1 (en) * | 1983-12-01 | 1985-10-03 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING AQUEOUS EMULSIONS |
-
1987
- 1987-09-10 DE DE19873730413 patent/DE3730413A1/en not_active Withdrawn
-
1988
- 1988-08-26 US US07/240,040 patent/US4874662A/en not_active Expired - Lifetime
- 1988-09-08 KR KR1019880011594A patent/KR950003854B1/en not_active IP Right Cessation
- 1988-09-08 EP EP88114668A patent/EP0306935B1/en not_active Expired - Lifetime
- 1988-09-08 DE DE8888114668T patent/DE3872993D1/en not_active Expired - Lifetime
- 1988-09-08 JP JP63223684A patent/JPH0197279A/en active Granted
- 1988-09-08 AT AT88114668T patent/ATE78531T1/en not_active IP Right Cessation
- 1988-09-09 AU AU22037/88A patent/AU609875B2/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4098701A (en) * | 1976-06-26 | 1978-07-04 | Dow Corning Limited | Process for treating fibres |
US4639321A (en) * | 1985-01-22 | 1987-01-27 | The Procter And Gamble Company | Liquid detergent compositions containing organo-functional polysiloxanes |
DE3503457A1 (en) * | 1985-02-01 | 1986-08-07 | Wacker-Chemie GmbH, 8000 München | METHOD FOR IMPREGNATING ORGANIC FIBERS |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350604A2 (en) * | 1988-05-26 | 1990-01-17 | Toray Silicone Company, Limited | Fibre-treatment composition |
EP0350604A3 (en) * | 1988-05-26 | 1991-10-30 | Toray Silicone Company, Limited | Fibre-treatment composition |
EP0651089A1 (en) * | 1993-10-27 | 1995-05-03 | Dow Corning Toray Silicone Company, Limited | Adsorption treatment method of fibers |
EP0692567A1 (en) * | 1994-07-14 | 1996-01-17 | Wacker-Chemie GmbH | Amionofunctional organopolysiloxane |
Also Published As
Publication number | Publication date |
---|---|
JPH0197279A (en) | 1989-04-14 |
KR890005341A (en) | 1989-05-13 |
DE3730413A1 (en) | 1989-03-30 |
AU2203788A (en) | 1989-03-16 |
ATE78531T1 (en) | 1992-08-15 |
JPH0137515B2 (en) | 1989-08-08 |
AU609875B2 (en) | 1991-05-09 |
US4874662A (en) | 1989-10-17 |
EP0306935A3 (en) | 1989-12-27 |
DE3872993D1 (en) | 1992-08-27 |
EP0306935B1 (en) | 1992-07-22 |
KR950003854B1 (en) | 1995-04-20 |
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