US20030013803A1 - Shear stable aminosilicone emulsions - Google Patents
Shear stable aminosilicone emulsions Download PDFInfo
- Publication number
- US20030013803A1 US20030013803A1 US10/226,725 US22672502A US2003013803A1 US 20030013803 A1 US20030013803 A1 US 20030013803A1 US 22672502 A US22672502 A US 22672502A US 2003013803 A1 US2003013803 A1 US 2003013803A1
- Authority
- US
- United States
- Prior art keywords
- emulsion
- acid
- amine
- group
- process according
- 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.)
- Abandoned
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 95
- 229920013822 aminosilicone Polymers 0.000 title claims description 3
- -1 siloxanes Chemical class 0.000 claims abstract description 52
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims 1
- 125000005372 silanol group Chemical group 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 239000002253 acid Substances 0.000 description 33
- 239000003921 oil Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 150000007513 acids Chemical class 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010008 shearing Methods 0.000 description 8
- 239000006071 cream Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004753 textile Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 2
- OYIFNHCXNCRBQI-UHFFFAOYSA-N 2-aminoadipic acid Chemical compound OC(=O)C(N)CCCC(O)=O OYIFNHCXNCRBQI-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LOLKAJARZKDJTD-UHFFFAOYSA-N 4-Ethoxy-4-oxobutanoic acid Chemical compound CCOC(=O)CCC(O)=O LOLKAJARZKDJTD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229960002989 glutamic acid Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JDRMYOQETPMYQX-UHFFFAOYSA-M 4-methoxy-4-oxobutanoate Chemical compound COC(=O)CCC([O-])=O JDRMYOQETPMYQX-UHFFFAOYSA-M 0.000 description 1
- RUADGOLRFXTMCY-UHFFFAOYSA-N CC1CCC(C)C(O)C1 Chemical compound CC1CCC(C)C(O)C1 RUADGOLRFXTMCY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- HGINADPHJQTSKN-UHFFFAOYSA-N Monoethyl malonic acid Chemical compound CCOC(=O)CC(O)=O HGINADPHJQTSKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000002015 acyclic group Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- JDRMYOQETPMYQX-UHFFFAOYSA-N butanedioic acid monomethyl ester Natural products COC(=O)CCC(O)=O JDRMYOQETPMYQX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- QBMNPDGCXLRKEA-UHFFFAOYSA-N carboxy 2-aminoacetate Chemical compound NCC(=O)OC(O)=O QBMNPDGCXLRKEA-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Definitions
- the present invention relates to a shear stable aqueous emulsion of a polysiloxane containing at least one amino group per molecule and a mono acid.
- the present invention also relates to an aqueous emulsion which when applied to fibrous substrate imparts softness to the substrate.
- aqueous emulsions containing organomodified polysiloxanes are used in the textile and paper industry to impart softness to the substrates.
- the polysiloxane emulsions usually are applied to textiles and papers using a padder, a kiss roller or a spraying nozzle, thus the polysiloxane emulsions are subjected to a certain extent of shear depending on the application method. Since the polysiloxane emulsions are heterogeneous mixtures containing small droplets of polysiloxane oils in water, coalescence of oil droplets to cream or surface oil occurs when the shear condition is severe enough.
- the present invention provides a method for the preparation of a shear stable aqueous emulsion comprising a polysiloxane containing at least one amino group per molecule (Aamino polysiloxane@), and a mono acid.
- the aqueous emulsion when applied to a fibrous substrate, imparts softness to the substrate.
- Preferred acids used herein include, but are not limited to (a) hydroxy carboxylic acids; (b) amino dicarboxylic acids; (c) amic acids; (d) monoesters of dicarboxylic acids; (e) monoesters of di-inorganic acids; and (f) diesters of tri-inorganic acids.
- the aminopolysiloxane has at least one amino or substituted amino group linked to a siloxy unit through an organic bridge that is bonded to the silicon atom of the siloxy unit by a carbon-to-silicon bond.
- the aminopolysiloxanes may be linear, branched or cyclic. They may have a viscosity ranging from about 1 to 20,000 centipoises measured at 25° C., preferably, about 10 to 10,000 at 25° C.
- the aminopolysiloxanes preferably have an amine content ranging from about 0.05% to 3%, by weight, preferably from about 0.1% to 2% by weight as measured as NH 2 .
- the aminopolysiloxanes may contain other functionalities, e.g., polyether.
- the aminopolysiloxane may be linear or branched or even by alternating linkages of aminoalkyl functionality and siloxane functionality; however, they should not contain reactive silanol (i.e., Si—OH) which would cause the aminopolysiloxane to crosslink in the emulsion.
- Q is a polyether, polyhydric, amine, epoxy, alkyl of C 2 -C 18 , or alkanol, but at least one Q is an amine containing group Z.
- V groups preferably are alkyl (which may be branched, linear or cyclic) of less than 8 carbons, which may or may not contain hydroxyl functionalities.
- Another preferred V is an alkyl amine functionality, the nitrogen of which may be further substituted (e.g., with an alkyl) or be further alkoxylated.
- Exemplary V are ethyl, ethanol, propanol, methyl, and ethyl amine.
- B 1 has 2 to 6 carbon atoms.
- B may also be a hydroxyl-substituted acyclic alkylene group of two to eight carbon atoms and is illustrated by 2-hydroxypropylene, i.e., —CH 2 CH(OH)CH 2 —, or B is a hydroxyl-substituted cyclic alkylene group having no more than eight carbon atoms, e.g., 2-hydroxycyclohexylene,
- Q or B is a mixture of oxyalkylenes, it may be blocked or random.
- One skilled in the art will understand the advantages in the position of the oxyethylene relative to the oxypropylene, when the alkyleneoxide group is blocked.
- Preferred Z structures are wherein R is hydrogen or methyl, B 1 is a divalent organic group of 2 to 4 carbons, B is a divalent organic group of 2 to 4 carbons, in which at least one carbon radical contains a hydroxyl group, and V is 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, propyl, ethyl or methyl.
- Exemplary amine groups for Q are:
- Those functionalities with free hydroxyls may be further alkoxylated with ethylene oxide and propylene oxide.
- aminopolysiloxanes employed in the present invention are commercially available from Witco Corporation.
- aminopolysiloxanes used in the present invention can be prepared by the procedures disclosed in U.S. Pat Nos. 3,033,815; 3,146,250, 3,355,454 and 4,247,592.
- the mono acid of the present invention is selected from the group consisting of (i) inorganic mono acids; (ii) organic (i.e., carboxylic) mono acids and (iii) mixtures thereof.
- the acids need to be proton donors to the amine (pKa ⁇ 6) and therefore the inorganic acid must be a Bronstead acid and the organic acid a carboxylic acid.
- Illustrative inorganic mono acids include hydrochloric acid, perchloric acid and nitric acid.
- Mono inorganic acids which are preferred are those which are monoesters of a di-inorganic acid, e.g., HSO 4 R wherein R is an alkyl, alkaryl or aryl, or diesters of tri-inorganic acids, e.g., HPO 4 R 2 . It is noted that the salts of such acids do not function well as compared to the esters.
- the organic mono acids contain one equivalence of a carboxylic acid, i.e., of the structure R 5 C( ⁇ O)OH, wherein R 5 is hydrogen or a neutral monovalent hydrocarbon and includes alkyl such as methyl, ethyl, propyl, butyl and the like; aryl such as phenyl and tolyl; aralkyl such as benzyl; and groups wherein one or more hydrogen atoms of the above mentioned groups are substituted with hydroxy, or halogen.
- Illustrative organic mono acids include formic acid, and acetic acid.
- R 5 could include other acid groups (i.e., carboxyls), but in such a case the cumulative effect of the substitutions on R 5 should not result in any additional acid or base (i.e., for every carboxyl there must be an amine or the carboxyl must be substituted to form an ester or amide).
- classes of preferred organic acids are hydroxy carboxylic acids, monoesters of dicarboxylic acids, amic acids (monoamides of dicarboxylic acids) and amino dicarboxylic acids.
- Specific amino dicarboxylic acids are ⁇ -aminoadipic acid, aspartic acid, and glutamic acid.
- Specific hydroxy carboxylic acids are glycolic acid, lactic acid, ⁇ -hydroxybutyric acid, and hydroxybenzoic acid.
- Specific monoesters of dicarboxylic acids are monomethyl succinate, monoethyl succinate and monoethyl malonic acid.
- Specific examples of amic acids are N-methyl succiniamic acid and maliamic acid.
- Some optional additives in the emulsion are amino/epoxy/siloxy terpolymers, polyether modified polysiloxanes, solvents (alcohol, mineral oil, silicone oil, or glycol ethers (e.g., butyl cellusolve)), epoxy/polyether/siloxy terpolymers, preservatives, fillers, colorants, biocides, biostats, silicone antifoams, perfume, viscosity modifier; waxes (parafins or polyethylene), emoliants, binders (latex), self-dispersing hydrophilic softening agents and freeze thaw additives (e.g., glycols).
- solvents alcohol, mineral oil, silicone oil, or glycol ethers (e.g., butyl cellusolve)
- epoxy/polyether/siloxy terpolymers preservatives, fillers, colorants, biocides, biostats, silicone antifoams, perfume, visco
- the preparation of a shear stable emulsion is accomplished by the addition of the mono acid, preferably an aqueous solution of the water soluble mono acid, to an aqueous emulsion of the aminopolysiloxane with mixing or blending.
- the mixing or blending need not be under high shear or elevated temperature, but may be simple mixing.
- Typical emulsifiers which can be used in the preparation of the aminopolysiloxane emulsion include nonionic, amphoteric (including zwitterionic), cationic and anionic surfactants.
- nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, polyalkylene glycol, and polyalkylene glycol modified polysiloxanes.
- cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxide, and trialkyl hydroxyethylammonium methosulfate.
- amphoteric surfactants are betaine derivatives, imidazolines, N-alkyl iminodiesters, cocoamine oxide, and dicarboxylic carboxy glycinate.
- anionic surfactants include sulfate and sulfonate salts such as sodium alkylsulfate, alkanolammonium alkylsulfate, sodium alkylarylsulfonate and alkanolammonium alkylarylsulfonate.
- the surfactants should be present at 5-40% by weight based on the amount of amino polysiloxane, preferably 10 to 20 weight percent.
- the emulsion may be buffered with salts of the acid to be used to ensure the maintenance of the pH of the emulsion within 4.5 to 9.5, preferably 0.5 to 8.5.
- Suitable buffers include sodium acetate, sodium propionate, sodium glycolate, and sodium glutamate.
- the amount of the aminopolysiloxane in the total final emulsion ranges from 0.1 to 75 parts by weight based on 100 parts of the total emulsion, and preferably 1 to 40 parts by weight based on 100 parts of the total emulsion. At least about 0.01% to about 1.5% amine content based on the total weight of the total emulsion should be present. Preferably, the amine content ranges from about 0.05% to 1%, and most preferably it ranges from about 0.05% to 0.5%.
- the amount of the mono acid depends on the amine content of the total emulsion.
- the amount of the mono acid ranges from about 0.05 equivalents to about 1.5 equivalents for every equivalent amount of amine in the total emulsion.
- the amount of the mono acid ranges from 0.1 to 1 equivalent for every equivalent amount of amine in the total emulsion.
- the present invention results in shear stable aminopolysiloxane aqueous emulsions, i.e., emulsion which do not show any surface oil or creaming or after the shear stability.
- the particle size in the emulsion should be less than 1.0 ⁇ m, preferably less than 0.5 ⁇ m.
- the emulsion may be translucent or opaque.
- the shear stable emulsion composition can be diluted with water to a desired solids level and applied onto fibrous substrates (which can be woven or non-woven) such as textiles and papers. Suitable application methods include printing, spraying, dipping or kiss roll application.
- the composition may be applied as a concentrate, but it will be more common to prepare the emulsion at a higher solids content to reduce shipping and/or handling costs and then dilute the formulation with water just prior to use.
- the resulting treated substrate thus has properties such as softness and compression resistance.
- the fibrous substrate which can be treated with the emulsion of the present invention is exemplified by natural fibers such as cotton, flax, silk, cellulose and wool; synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; and inorganic fibers such as glass fiber and carbon fiber. Blends of any of the foregoing are also potential substrates.
- emulsions also may be use in personal care (e.g., hair care, and skin care products), car polishes, leather protectants, and shine and gloss protectants.
- personal care e.g., hair care, and skin care products
- car polishes e.g., hair care, and skin care products
- leather protectants e.g., leather protectants
- shine and gloss protectants e.g., shine and gloss protectants.
- the emulsion is applied onto tissue, paper towels, wipes, etc.
- Methods for such applications are disclosed in U.S. Pat. No. 5,573,637 to Ampulski; U.S. Pat. No. 5,389,204 to Ampulski; U.S. Pat. No. 5,246,546 to Ampulski; U.S. Pat. No. 5,215,626 to Ampulski; and U.S. Pat. No. 5,529,665 to Kaun, which are incorporated herein by reference.
- Test Method for Shear Stability The following method is used to determine the shear stability of an aminopolysiloxane emulsion.
- a shear stable aminopolysiloxane emulsion does not show any surface oil or creaming or after the shear stability.
- a 400 g sample of an aminopolysiloxane emulsion is placed in a plastic container with a 7.5 inch ( ⁇ 19 cm) inner diameter. The container then is placed under a Lightnin mixer mounted with a 6 inch ( ⁇ 15 cm) diameter Cowles blade. The sample is sheared with the Cowles blade at 2,000 rpm for 1 hour. The sheared emulsion is examined for surface oil and creaming.
- Creaming is a process of emulsion droplets floating upwards to form a concentrated emulsion (cream), quite distinct from the underlying dilute emulsion.
- Surface oil is when the emulsion droplets coalesce to form oil which then floats to the surface of the emulsion.
- Emulsion I was prepared by blending 50 parts of an aminopolysiloxane of 40,000 molecular weight which contains 0.25% by weight amine, 40.7 parts of water and 9.3 parts of a blend of polyethyleneoxide alkyl ethers having an HLB of 12-13.
- Emulsion I To 60 parts of Emulsion I, 0.5 part of a 10% aqueous HCl solution, 1 part of a 10% aqueous NaCl solution and 38.5 parts of water were added. The resulting emulsion was milky white and stable at room temperature. No creaming or surface oil was detected in the sheared emulsion. The sheared emulsion maintained one phase and stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 40 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing, the emulsion broke down to three phases: (1) surface oil which amounts to approximately 10% of the total material, (2) cream phase which amounts to about 10% of the total material, and (3) emulsion phase which amounts to about 80% of the total material.
- Emulsion I To 60 parts of Emulsion I, 0.7 part of a 10% aqueous sulfuric acid solution, 1 part of a 10% aqueous sodium sulfate solution and 38.3 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After the shear test, the emulsion broke down to three phases: (1) some surface oil floating on top of the cream phase, (2) cream phase which amounts to about 50% of the total material, and (3) emulsion phase which amounts to about 50% of the total material.
- Emulsion I To 60 parts of Emulsion I, 2.3 parts of a 10% aqueous glycolic acid solution, 0.4 parts of a 10% aqueous sodium hydroxide solution and 37.3 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing, no creaming or surface oil was detected. The emulsion maintained its homogeneous translucent appearance and was stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 2.4 parts of a 10% aqueous succinic acid solution, 0.5 parts of a 10% aqueous sodium hydroxide solution and 37.1 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After the shear test, the emulsion broke down to three phases: (1) some surface oil floating on top of the cream phase, (2) cream phase which amounts to about 40% of the total material, and (3) emulsion phase which amounts to about 60% of the total material.
- Emulsion I To 60 parts of Emulsion I, 1.5 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution and 37.5 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion had a homogeneous translucent appearance and was stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 3 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution and 36 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained its homogeneous appearance and was stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 26.8 parts of a 0.75% aqueous solution of L-glutamic acid, 1 part of a 10% aqueous sodium glutamate solution and 12.2 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained one phase and stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 28.6 parts of a 1% aqueous hydroxybenzoic acid solution, 1 part of a 10% aqueous sodium hydroxide and 11.1 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected in the sheared emulsion. The emulsion maintained one phase and stable at room temperature.
- Emulsion I To 60 parts of Emulsion I, 1.5 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution, 1 part of a 12,500 molecular weight polyoxyalkylene polysiloxane copolymer which is 88% by weight polyether, and 36.5 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained its homogeneous translucent appearance and stable at room temperature.
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Epidemiology (AREA)
- Dispersion Chemistry (AREA)
- Birds (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Aqueous emulsions of amino modified siloxanes may be made shear stable by the addition of at least one hydroxy carboxylic acid to the emulsion.
Description
- This application is a continuation of U.S. application Ser. No. 09/250,330, filed Feb. 16, 1999.
- The present invention relates to a shear stable aqueous emulsion of a polysiloxane containing at least one amino group per molecule and a mono acid. The present invention also relates to an aqueous emulsion which when applied to fibrous substrate imparts softness to the substrate.
- Many aqueous emulsions containing organomodified polysiloxanes are used in the textile and paper industry to impart softness to the substrates. The polysiloxane emulsions usually are applied to textiles and papers using a padder, a kiss roller or a spraying nozzle, thus the polysiloxane emulsions are subjected to a certain extent of shear depending on the application method. Since the polysiloxane emulsions are heterogeneous mixtures containing small droplets of polysiloxane oils in water, coalescence of oil droplets to cream or surface oil occurs when the shear condition is severe enough. This not only causes problems in the manufacturing process, it also may result in deposit of the polysiloxane oils on textiles and papers and increase rejects. Therefore, a shear stable polysiloxane emulsion is very important in the application of polysiloxane emulsions.
- The use of certain acids, e.g., citric acid, in the preparation of aminosilicone emulsions is known, but only to modify the pH of the emulsion, not to impart any stability to it. See e.g., U.S. Pat. No. 4,601,902 to Fridd et al. Acids also have been used to neutralize catalysts in emulsion polymerization systems containing aminosiloxanes, but the aminosiloxane herein are cross-linkable, reactive species, and the the neutralization is of the catalyst, not the siloxane or the emulsion. See, e.g., U.S. Pat. No. 4,894,412 to Okada et al. The selection of the particular acid is important in that certain acids will not provide benefits for shearing properties of the emulsion.
- The present invention provides a method for the preparation of a shear stable aqueous emulsion comprising a polysiloxane containing at least one amino group per molecule (Aamino polysiloxane@), and a mono acid. The aqueous emulsion, when applied to a fibrous substrate, imparts softness to the substrate. Preferred acids used herein, include, but are not limited to (a) hydroxy carboxylic acids; (b) amino dicarboxylic acids; (c) amic acids; (d) monoesters of dicarboxylic acids; (e) monoesters of di-inorganic acids; and (f) diesters of tri-inorganic acids.
- Aminopolysiloxane
- The aminopolysiloxane has at least one amino or substituted amino group linked to a siloxy unit through an organic bridge that is bonded to the silicon atom of the siloxy unit by a carbon-to-silicon bond. The aminopolysiloxanes may be linear, branched or cyclic. They may have a viscosity ranging from about 1 to 20,000 centipoises measured at 25° C., preferably, about 10 to 10,000 at 25° C. The aminopolysiloxanes preferably have an amine content ranging from about 0.05% to 3%, by weight, preferably from about 0.1% to 2% by weight as measured as NH2. The aminopolysiloxanes may contain other functionalities, e.g., polyether. The aminopolysiloxane may be linear or branched or even by alternating linkages of aminoalkyl functionality and siloxane functionality; however, they should not contain reactive silanol (i.e., Si—OH) which would cause the aminopolysiloxane to crosslink in the emulsion. The preferred aminopolysiloxane is a linear structure illustrated by Formula MDaD*bM wherein D is O1/2Si(CH3)2O1/2; D* is O1/2Si(CH3)QO1/2; and M is O1/2SiQj(CH3)3−j, a ranges in value from about 0 to 1,000, and most preferably a ranges in value from about 0 to 500; j=0 or 1; and b ranges in value from about 0 to 100, preferably b ranges in value from about 1 to 50, most preferably b ranges in value from about 1 to 20, b+j>0 and a/(b+j) is 0.5 to 5.
- Q is a polyether, polyhydric, amine, epoxy, alkyl of C2-C18, or alkanol, but at least one Q is an amine containing group Z. The group Z may be of the formula BN[B1O(CdH2dO)eR]2−zVz, where each d is 2 to 4, preferably 2 to 3, each e is 0 to 15, preferably 0 to 8, z=0 to 2, preferably 2, each V is a univalent group, B1 is an alkylene divalent bridging group on which there may be hydroxyl substituents, and B is a divalent bridging group.
- V groups preferably are alkyl (which may be branched, linear or cyclic) of less than 8 carbons, which may or may not contain hydroxyl functionalities. Another preferred V is an alkyl amine functionality, the nitrogen of which may be further substituted (e.g., with an alkyl) or be further alkoxylated. Exemplary V are ethyl, ethanol, propanol, methyl, and ethyl amine.
-
- of which the cyclic groups having three to six carbon atoms are preferred.
- When Q or B is a mixture of oxyalkylenes, it may be blocked or random. One skilled in the art will understand the advantages in the position of the oxyethylene relative to the oxypropylene, when the alkyleneoxide group is blocked.
- Also contemplated herein are quaternary versions of Z, but said quaternary compounds are not preferred for use in the present invention.
- Preferred Z structures are wherein R is hydrogen or methyl, B1 is a divalent organic group of 2 to 4 carbons, B is a divalent organic group of 2 to 4 carbons, in which at least one carbon radical contains a hydroxyl group, and V is 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, propyl, ethyl or methyl. Exemplary amine groups for Q are:
- —C3H6NH2
- —C3H6N(C2H5)2
- —CH2CH2C(CH3)2NH2
- —C3H6N(CH2CH2OH)2
- —C3H6N(CH3)CH2CH2NH2
- —C3H6NHCH2CH2NH2
- —C3H6OCH2CH(OH)CH2NH2
- —C3H6—N(CH2CH2OH)(CH2CH2NH2)
- —C3H6OCH2CH(OH)CH2NHCH2CH2NH2
- Those functionalities with free hydroxyls may be further alkoxylated with ethylene oxide and propylene oxide.
- Aminopolysiloxanes employed in the present invention are commercially available from Witco Corporation. Alternatively, aminopolysiloxanes used in the present invention can be prepared by the procedures disclosed in U.S. Pat Nos. 3,033,815; 3,146,250, 3,355,454 and 4,247,592.
- Mono Acid
- Mono acids which are soluble or dispersible in water and thus, compatible with the aqueous emulsion containing the aminopolysiloxane can be employed in the present invention. In its broadest aspect, the mono acid of the present invention is selected from the group consisting of (i) inorganic mono acids; (ii) organic (i.e., carboxylic) mono acids and (iii) mixtures thereof. The acids need to be proton donors to the amine (pKa<6) and therefore the inorganic acid must be a Bronstead acid and the organic acid a carboxylic acid. Illustrative inorganic mono acids include hydrochloric acid, perchloric acid and nitric acid.
- Mono inorganic acids which are preferred are those which are monoesters of a di-inorganic acid, e.g., HSO4R wherein R is an alkyl, alkaryl or aryl, or diesters of tri-inorganic acids, e.g., HPO4R2. It is noted that the salts of such acids do not function well as compared to the esters.
- The organic mono acids contain one equivalence of a carboxylic acid, i.e., of the structure R5C(═O)OH, wherein R5 is hydrogen or a neutral monovalent hydrocarbon and includes alkyl such as methyl, ethyl, propyl, butyl and the like; aryl such as phenyl and tolyl; aralkyl such as benzyl; and groups wherein one or more hydrogen atoms of the above mentioned groups are substituted with hydroxy, or halogen. Illustrative organic mono acids include formic acid, and acetic acid.
- R5 could include other acid groups (i.e., carboxyls), but in such a case the cumulative effect of the substitutions on R5 should not result in any additional acid or base (i.e., for every carboxyl there must be an amine or the carboxyl must be substituted to form an ester or amide). For example, classes of preferred organic acids are hydroxy carboxylic acids, monoesters of dicarboxylic acids, amic acids (monoamides of dicarboxylic acids) and amino dicarboxylic acids. Specific amino dicarboxylic acids are α-aminoadipic acid, aspartic acid, and glutamic acid. Specific hydroxy carboxylic acids are glycolic acid, lactic acid, β-hydroxybutyric acid, and hydroxybenzoic acid. Specific monoesters of dicarboxylic acids are monomethyl succinate, monoethyl succinate and monoethyl malonic acid. Specific examples of amic acids are N-methyl succiniamic acid and maliamic acid.
- Optional Additives
- Some optional additives in the emulsion are amino/epoxy/siloxy terpolymers, polyether modified polysiloxanes, solvents (alcohol, mineral oil, silicone oil, or glycol ethers (e.g., butyl cellusolve)), epoxy/polyether/siloxy terpolymers, preservatives, fillers, colorants, biocides, biostats, silicone antifoams, perfume, viscosity modifier; waxes (parafins or polyethylene), emoliants, binders (latex), self-dispersing hydrophilic softening agents and freeze thaw additives (e.g., glycols).
- Emulsion Preparation
- The preparation of a shear stable emulsion is accomplished by the addition of the mono acid, preferably an aqueous solution of the water soluble mono acid, to an aqueous emulsion of the aminopolysiloxane with mixing or blending. The mixing or blending need not be under high shear or elevated temperature, but may be simple mixing.
- The preparations of the emulsion of the aminopolysiloxane are known in the art. A preferred way to do this is by adding the aminosiloxane slowly under high shear to a water/surfactant mixture until a fine grease is formed. Water should be added then to invert the emulsion to form an oil in water emulsion. Lastly, the acid should be added.
- Typical emulsifiers which can be used in the preparation of the aminopolysiloxane emulsion include nonionic, amphoteric (including zwitterionic), cationic and anionic surfactants. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, polyalkylene glycol, and polyalkylene glycol modified polysiloxanes. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxide, and trialkyl hydroxyethylammonium methosulfate. Examples of amphoteric surfactants are betaine derivatives, imidazolines, N-alkyl iminodiesters, cocoamine oxide, and dicarboxylic carboxy glycinate. Examples of anionic surfactants include sulfate and sulfonate salts such as sodium alkylsulfate, alkanolammonium alkylsulfate, sodium alkylarylsulfonate and alkanolammonium alkylarylsulfonate. Specific examples are SPAN (ICI), TWEEN (ICI), WITCONOL (Witco), REWOTERIC (Witco) and tridecyl alcohol ethoxylates. The surfactants should be present at 5-40% by weight based on the amount of amino polysiloxane, preferably 10 to 20 weight percent.
- The emulsion may be buffered with salts of the acid to be used to ensure the maintenance of the pH of the emulsion within 4.5 to 9.5, preferably 0.5 to 8.5. Suitable buffers include sodium acetate, sodium propionate, sodium glycolate, and sodium glutamate.
- The amount of the aminopolysiloxane in the total final emulsion ranges from 0.1 to 75 parts by weight based on 100 parts of the total emulsion, and preferably 1 to 40 parts by weight based on 100 parts of the total emulsion. At least about 0.01% to about 1.5% amine content based on the total weight of the total emulsion should be present. Preferably, the amine content ranges from about 0.05% to 1%, and most preferably it ranges from about 0.05% to 0.5%.
- The amount of the mono acid depends on the amine content of the total emulsion. The amount of the mono acid ranges from about 0.05 equivalents to about 1.5 equivalents for every equivalent amount of amine in the total emulsion. Preferably, the amount of the mono acid ranges from 0.1 to 1 equivalent for every equivalent amount of amine in the total emulsion. Most preferably, there should be a molar equivalency of acid functionality to amino functionality.
- Emulsion Application to Textiles and Papers
- The present invention results in shear stable aminopolysiloxane aqueous emulsions, i.e., emulsion which do not show any surface oil or creaming or after the shear stability. The particle size in the emulsion should be less than 1.0 μm, preferably less than 0.5 μm. The emulsion may be translucent or opaque.
- The shear stable emulsion composition can be diluted with water to a desired solids level and applied onto fibrous substrates (which can be woven or non-woven) such as textiles and papers. Suitable application methods include printing, spraying, dipping or kiss roll application. The composition may be applied as a concentrate, but it will be more common to prepare the emulsion at a higher solids content to reduce shipping and/or handling costs and then dilute the formulation with water just prior to use. After the substrate is dried either at room temperature or by heat, it additionally can be optionally cured to crosslink at a temperature less than the melting or decomposition temperature of the substrate. Heating can be done by any suitable method, but preferably is done by passing the substrate through a hot air oven. The resulting treated substrate thus has properties such as softness and compression resistance.
- The fibrous substrate which can be treated with the emulsion of the present invention is exemplified by natural fibers such as cotton, flax, silk, cellulose and wool; synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; and inorganic fibers such as glass fiber and carbon fiber. Blends of any of the foregoing are also potential substrates.
- These emulsions also may be use in personal care (e.g., hair care, and skin care products), car polishes, leather protectants, and shine and gloss protectants. Preferably, the emulsion is applied onto tissue, paper towels, wipes, etc. Methods for such applications are disclosed in U.S. Pat. No. 5,573,637 to Ampulski; U.S. Pat. No. 5,389,204 to Ampulski; U.S. Pat. No. 5,246,546 to Ampulski; U.S. Pat. No. 5,215,626 to Ampulski; and U.S. Pat. No. 5,529,665 to Kaun, which are incorporated herein by reference.
- The following examples are set forth to illustrative purposes only and not to be construed as unduly limiting of the present invention. All parts and percentages are by weight unless otherwise specified.
- Test Method for Shear Stability: The following method is used to determine the shear stability of an aminopolysiloxane emulsion. A shear stable aminopolysiloxane emulsion does not show any surface oil or creaming or after the shear stability. A 400 g sample of an aminopolysiloxane emulsion is placed in a plastic container with a 7.5 inch (˜19 cm) inner diameter. The container then is placed under a Lightnin mixer mounted with a 6 inch (˜15 cm) diameter Cowles blade. The sample is sheared with the Cowles blade at 2,000 rpm for 1 hour. The sheared emulsion is examined for surface oil and creaming.
- Creaming is a process of emulsion droplets floating upwards to form a concentrated emulsion (cream), quite distinct from the underlying dilute emulsion. Surface oil is when the emulsion droplets coalesce to form oil which then floats to the surface of the emulsion.
- Emulsion I was prepared by blending 50 parts of an aminopolysiloxane of 40,000 molecular weight which contains 0.25% by weight amine, 40.7 parts of water and 9.3 parts of a blend of polyethyleneoxide alkyl ethers having an HLB of 12-13.
- To 60 parts of Emulsion I, 0.5 part of a 10% aqueous HCl solution, 1 part of a 10% aqueous NaCl solution and 38.5 parts of water were added. The resulting emulsion was milky white and stable at room temperature. No creaming or surface oil was detected in the sheared emulsion. The sheared emulsion maintained one phase and stable at room temperature.
- To 60 parts of Emulsion I, 40 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing, the emulsion broke down to three phases: (1) surface oil which amounts to approximately 10% of the total material, (2) cream phase which amounts to about 10% of the total material, and (3) emulsion phase which amounts to about 80% of the total material.
- To 60 parts of Emulsion I, 0.7 part of a 10% aqueous sulfuric acid solution, 1 part of a 10% aqueous sodium sulfate solution and 38.3 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After the shear test, the emulsion broke down to three phases: (1) some surface oil floating on top of the cream phase, (2) cream phase which amounts to about 50% of the total material, and (3) emulsion phase which amounts to about 50% of the total material.
- To 60 parts of Emulsion I, 2.3 parts of a 10% aqueous glycolic acid solution, 0.4 parts of a 10% aqueous sodium hydroxide solution and 37.3 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing, no creaming or surface oil was detected. The emulsion maintained its homogeneous translucent appearance and was stable at room temperature.
- To 60 parts of Emulsion I, 2.4 parts of a 10% aqueous succinic acid solution, 0.5 parts of a 10% aqueous sodium hydroxide solution and 37.1 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After the shear test, the emulsion broke down to three phases: (1) some surface oil floating on top of the cream phase, (2) cream phase which amounts to about 40% of the total material, and (3) emulsion phase which amounts to about 60% of the total material.
- To 60 parts of Emulsion I, 1.5 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution and 37.5 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion had a homogeneous translucent appearance and was stable at room temperature.
- To 60 parts of Emulsion I, 3 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution and 36 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained its homogeneous appearance and was stable at room temperature.
- To 60 parts of Emulsion I, 26.8 parts of a 0.75% aqueous solution of L-glutamic acid, 1 part of a 10% aqueous sodium glutamate solution and 12.2 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained one phase and stable at room temperature.
- To 60 parts of Emulsion I, 28.6 parts of a 1% aqueous hydroxybenzoic acid solution, 1 part of a 10% aqueous sodium hydroxide and 11.1 parts of water were added. The resulting emulsion was milky white and stable at room temperature. After shearing no creaming or surface oil was detected in the sheared emulsion. The emulsion maintained one phase and stable at room temperature.
- To 60 parts of Emulsion I, 1.5 parts of a 10% aqueous acetic acid solution, 1 part of a 10% aqueous sodium acetate solution, 1 part of a 12,500 molecular weight polyoxyalkylene polysiloxane copolymer which is 88% by weight polyether, and 36.5 parts of water were added. The resulting emulsion was translucent and stable at room temperature. After shearing no creaming or surface oil was detected. The emulsion maintained its homogeneous translucent appearance and stable at room temperature.
Claims (16)
1. A shear stable aminosilicone emulsion composition comprising:
a. water;
b. emulsifier
b. an amino polysiloxane; and
c. at least one hydroxy carboxylic acid.
2. A composition according to claim 1 wherein the siloxane has a viscosity of from about 1 to 20,000 centipoises measured at 25° C., an amine content ranging from about 0.01% to 3% and has no silanol groups.
3. A composition according to claim 2 wherein the siloxane is MDaD*bM wherein D is O1/2Si(CH3)2O1/2; wherein D* is O1/2Si(CH3)QO1/2; and M is O1/2SiQj(CH3)3−j., a ranges in value from about 30 to 600, j=0 or 1; and b ranges in value from about 0 to 100, b+j>0 and a/(b+j) is 0.5 to 5, Q is a polyether, polyhydric, amine, epoxy, alkyl of C2-C18, or alkanol, but at least one Q is an amine, which amine may be of the formula, BN[B1O(CdH2dO)eR]2−zVz, each d is 2 to 4, each e is 0 to 15, z is 0 to 2, each V is a univalent group, B1 is an alkylene divalent bridging group on which there may be hydroxyl substituents, and B is a divalent bridging group.
4. A composition according to claim 1 wherein the hydroxy carboxylic acid is selected from the group consisting of glycolic acid, lactic acid, β-hydroxybutyric acid, and hydroxybenzoic acid.
5. A composition according to claim 1 wherein the amino polysiloxane has a polyether functionality.
6. A composition according to claim 1 wherein the emulsifier consists essentially of one or more non-ionic surfactants.
7. A composition according to claim 1 wherein the emulsifier is selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyalkylene glycol and polyalkylene glycol modified polysiloxanes.
8. A process which comprises:
providing an aqueous emulsion comprising an emulsifier and an amino polysiloxane; and
adding a shear stabilizing effective amount of at least one hydroxy carboxylic acid to the emulsion to impart shear stability to the emulsion.
9. The process of claim 8 wherein the amino polysiloxane corresponds to the formula MDaD*bM wherein D is O1/2Si(CH3)2O1/2; wherein D* is O1/2Si(CH3)QO1/2; and M is O1/2SiQj(CH3)3−j, a ranges in value from about 30 to 600, j=0 or 1; and b ranges in value from about 0 to 100, b+j>0 and a/(b+j) is 0.5 to 5, Q is a polyether, polyhydric, amine, epoxy, alkyl of C2-C18, or alkanol, but at least one Q is an amine, which amine may be of the formula, BN[B1O(CdH2dO)eR]2−zVz, d is 2 to 4, e is 0 to 15, z is 0 to 2, V is a univalent group, B1 is an alkylene divalent bridging group on which there may be hydroxyl substituents, and B is a divalent bridging group.
10. A process according to claim 8 additionally comprising applying the shear stabilized emulsion to a substrate.
11. A process according to claim 10 wherein the substrate is a cellulosic fabric.
12. A process according to claim 8 wherein the hydroxy carboxylic acid is selected from the group consisting of glycolic acid, lactic acid, β-hydroxybutyric acid, and hydroxybenzoic acid.
13. A process according to claim 8 wherein the amino polysiloxane has polyether functionality.
14. A process according to claim 8 wherein the emulsifier consists essentially of one or more non-ionic surfactants.
15. A process according to claim 8 wherein the emulsifier is selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyalkylene glycol and polyalkylene glycol modified polysiloxanes.
16. A process according to claim 8 wherein the hydroxy carboxylic acid is glycolic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/226,725 US20030013803A1 (en) | 1999-02-16 | 2002-08-22 | Shear stable aminosilicone emulsions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/250,330 US6451905B2 (en) | 1999-02-16 | 1999-02-16 | Shear stable aminosilicone emulsions |
US10/226,725 US20030013803A1 (en) | 1999-02-16 | 2002-08-22 | Shear stable aminosilicone emulsions |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/250,330 Continuation US6451905B2 (en) | 1999-02-16 | 1999-02-16 | Shear stable aminosilicone emulsions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030013803A1 true US20030013803A1 (en) | 2003-01-16 |
Family
ID=22947297
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/250,330 Expired - Fee Related US6451905B2 (en) | 1999-02-16 | 1999-02-16 | Shear stable aminosilicone emulsions |
US10/226,725 Abandoned US20030013803A1 (en) | 1999-02-16 | 2002-08-22 | Shear stable aminosilicone emulsions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/250,330 Expired - Fee Related US6451905B2 (en) | 1999-02-16 | 1999-02-16 | Shear stable aminosilicone emulsions |
Country Status (7)
Country | Link |
---|---|
US (2) | US6451905B2 (en) |
EP (1) | EP1151042A1 (en) |
JP (1) | JP2002537434A (en) |
KR (1) | KR100712759B1 (en) |
BR (1) | BR0008255A (en) |
CA (1) | CA2362197A1 (en) |
WO (1) | WO2000049090A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080019939A1 (en) * | 2006-07-20 | 2008-01-24 | Alberto-Culver Company | Conditioner formulation |
CN109293946A (en) * | 2018-10-12 | 2019-02-01 | 浙江科峰新材料有限公司 | A kind of amido silicon oil emulsifier special |
CN109467718A (en) * | 2018-10-12 | 2019-03-15 | 浙江科峰新材料有限公司 | A kind of preparation method and application of amido silicon oil emulsifier special |
US11466400B2 (en) * | 2018-06-19 | 2022-10-11 | Hexcel Corporation | Finish composition |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10105234A1 (en) * | 2001-02-02 | 2002-08-29 | Schoeller Textil Ag Sevelen | Textile surface |
JP2005505642A (en) * | 2001-07-19 | 2005-02-24 | ハンツマン・インターナショナル・エルエルシー | Release agent for lignocellulose composite material |
DE10163860A1 (en) * | 2001-12-22 | 2003-07-10 | Henkel Kgaa | Use of selected short chain carboxylic acids |
US20050013785A1 (en) * | 2003-04-14 | 2005-01-20 | The Procter & Gamble Company | Anhydrous, silicone modified fluorinated polymers for transfer-resistant cosmetic lip compositions |
WO2004091561A1 (en) * | 2003-04-14 | 2004-10-28 | The Procter & Gamble Company | Transfer-resistant cosmetic compositions |
WO2004091559A2 (en) * | 2003-04-14 | 2004-10-28 | The Procter & Gamble Company | Anhydrous, transfer-resistant cosmetic lip compositions |
US7279519B2 (en) * | 2004-03-22 | 2007-10-09 | General Electric Company | Composition and method for treating textiles |
JP4822892B2 (en) * | 2005-09-09 | 2011-11-24 | 信越化学工業株式会社 | Coating agent |
GB0611217D0 (en) * | 2006-06-08 | 2006-07-19 | Dow Corning | Amino-acid functional siloxanes,methods of preparation and applications |
WO2011042409A2 (en) | 2009-10-05 | 2011-04-14 | Momentive Performance Materials Gmbh | Aqueous emulsions of polyorganosiloxanes |
DE102011085492A1 (en) | 2011-10-31 | 2013-05-02 | Evonik Goldschmidt Gmbh | New amino group-containing siloxanes, process for their preparation and use |
WO2014193636A1 (en) * | 2013-05-31 | 2014-12-04 | Dow Corning Corporation | Process for preparing aminofunctional silicone emulsions |
US20220218589A1 (en) * | 2019-05-29 | 2022-07-14 | Wacker Chemie Ag | Aqueous dispersions of pre-crosslinked organopolysiloxanes |
CN111690275B (en) * | 2020-07-10 | 2022-03-08 | 清远市宏图助剂有限公司 | Durable-high-adhesion ceramic tile antifouling liquid and using method thereof |
CN114232139A (en) * | 2021-12-16 | 2022-03-25 | 连云港神鹰复合材料科技有限公司 | Preparation method of carbon fiber oil for dry-jet wet-spun precursor |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4601902A (en) * | 1983-07-30 | 1986-07-22 | Dow Corning Ltd. | Compositions and process for treating hair |
US4620878A (en) * | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
US4894412A (en) * | 1987-05-19 | 1990-01-16 | Shin-Etsu Chemical Co., Ltd. | Process for preparing self-crosslinkable aminosiloxane emulsion |
US5571442A (en) * | 1995-02-01 | 1996-11-05 | Matsumoto Yushi-Seiyaku Co., Ltd. | Textile treating composition |
US5573694A (en) * | 1989-09-07 | 1996-11-12 | Sandoz Ltd. | Microemulsions of aminopolysiloxanes |
US5683625A (en) * | 1994-05-27 | 1997-11-04 | General Electric Company | Method of preparing microemulsions |
US5712343A (en) * | 1993-08-27 | 1998-01-27 | Wacker-Chemie Gmbh | Preparation of organopolysiloxane microemulsions |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3723697A1 (en) * | 1987-04-24 | 1988-11-17 | Pfersee Chem Fab | AQUEOUS, FINE-PARTIC TO OPTICALLY CLEAR, THERMALLY AND MECHANICALLY STABLE SILICONE EMULSIONS, METHOD FOR THE PRODUCTION AND USE THEREOF |
JPH0655817B2 (en) * | 1989-04-27 | 1994-07-27 | 信越化学工業株式会社 | Method for producing aminosilicone fine particle emulsion |
JP2750899B2 (en) * | 1989-06-19 | 1998-05-13 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing cyclohexylamino group-containing organopolysiloxane microemulsion |
JP3266367B2 (en) * | 1993-04-28 | 2002-03-18 | 東レ・ダウコーニング・シリコーン株式会社 | Silicone emulsion composition for wiping paper |
US6180117B1 (en) * | 1994-05-27 | 2001-01-30 | General Electric Company | Method of preparing microemulsions of amino silicone fluids and MQ resin mixtures |
JP3495110B2 (en) * | 1994-09-09 | 2004-02-09 | 日本ユニカー株式会社 | Amino group-containing organopolysiloxane microemulsion and process for producing the same |
JP3120719B2 (en) * | 1995-11-20 | 2000-12-25 | 信越化学工業株式会社 | Fiber treatment composition |
JP3602633B2 (en) * | 1995-12-28 | 2004-12-15 | 日本ユニカー株式会社 | Aqueous cosmetic containing amino-modified polysiloxane-polyoxyalkylene block copolymer |
US5856544A (en) * | 1996-04-15 | 1999-01-05 | Osi Specialties, Inc. | Aminopolysiloxanes with hindered 4-amino-3,3-dimethylbutyl groups |
US5707435A (en) * | 1996-10-16 | 1998-01-13 | Dow Corning Corporation | Ammonium siloxane emulsions and their use as fiber treatment agents |
US5707434A (en) * | 1996-10-16 | 1998-01-13 | Dow Corning Corporation | Water soluble ammonium siloxane compositions and their use as fiber treatment agents |
-
1999
- 1999-02-16 US US09/250,330 patent/US6451905B2/en not_active Expired - Fee Related
-
2000
- 2000-02-14 KR KR1020017010050A patent/KR100712759B1/en not_active IP Right Cessation
- 2000-02-14 WO PCT/US2000/003770 patent/WO2000049090A1/en active IP Right Grant
- 2000-02-14 BR BR0008255-4A patent/BR0008255A/en not_active Application Discontinuation
- 2000-02-14 EP EP00911799A patent/EP1151042A1/en not_active Withdrawn
- 2000-02-14 CA CA002362197A patent/CA2362197A1/en not_active Abandoned
- 2000-02-14 JP JP2000599823A patent/JP2002537434A/en active Pending
-
2002
- 2002-08-22 US US10/226,725 patent/US20030013803A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4601902A (en) * | 1983-07-30 | 1986-07-22 | Dow Corning Ltd. | Compositions and process for treating hair |
US4620878A (en) * | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
US4894412A (en) * | 1987-05-19 | 1990-01-16 | Shin-Etsu Chemical Co., Ltd. | Process for preparing self-crosslinkable aminosiloxane emulsion |
US5573694A (en) * | 1989-09-07 | 1996-11-12 | Sandoz Ltd. | Microemulsions of aminopolysiloxanes |
US5712343A (en) * | 1993-08-27 | 1998-01-27 | Wacker-Chemie Gmbh | Preparation of organopolysiloxane microemulsions |
US5683625A (en) * | 1994-05-27 | 1997-11-04 | General Electric Company | Method of preparing microemulsions |
US5571442A (en) * | 1995-02-01 | 1996-11-05 | Matsumoto Yushi-Seiyaku Co., Ltd. | Textile treating composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080019939A1 (en) * | 2006-07-20 | 2008-01-24 | Alberto-Culver Company | Conditioner formulation |
US11466400B2 (en) * | 2018-06-19 | 2022-10-11 | Hexcel Corporation | Finish composition |
CN109293946A (en) * | 2018-10-12 | 2019-02-01 | 浙江科峰新材料有限公司 | A kind of amido silicon oil emulsifier special |
CN109467718A (en) * | 2018-10-12 | 2019-03-15 | 浙江科峰新材料有限公司 | A kind of preparation method and application of amido silicon oil emulsifier special |
Also Published As
Publication number | Publication date |
---|---|
EP1151042A1 (en) | 2001-11-07 |
BR0008255A (en) | 2002-01-15 |
WO2000049090A1 (en) | 2000-08-24 |
US20010047052A1 (en) | 2001-11-29 |
CA2362197A1 (en) | 2000-08-24 |
JP2002537434A (en) | 2002-11-05 |
US6451905B2 (en) | 2002-09-17 |
KR20010108189A (en) | 2001-12-07 |
KR100712759B1 (en) | 2007-05-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6451905B2 (en) | Shear stable aminosilicone emulsions | |
AU624263B2 (en) | Stable emulsions containing amino polysiloxanes and silanes for treating fibers and fabrics | |
US5707435A (en) | Ammonium siloxane emulsions and their use as fiber treatment agents | |
EP0924240B1 (en) | Organopolysiloxane emulsions | |
KR950003850B1 (en) | Fiber treatment agent | |
EP0803527B1 (en) | Aminopolysiloxanes with hindered 4-amino-3,3-dimethyl-butyl groups | |
US5417867A (en) | Fiber treatment agent | |
US7329707B2 (en) | Partially quaternised, amino-functional organopolysiloxanes and their use in aqueous systems | |
JP2004528412A (en) | Organopolysiloxane composition, method for producing emulsion-forming organopolysiloxane composition, and method for treating fiber or fabric of textile product | |
JP5743284B2 (en) | Self-emulsifying microemulsion composition and fiber treatment agent | |
JPH0284580A (en) | Treating agent for knitted or woven fabric or the like and treated textile product, such as knitted or woven fabric | |
JP2017197863A (en) | Film formative silicone emulsion composition | |
ES2680943T3 (en) | Polysiloxanes with quaternized heterocyclic groups | |
JP2001342351A (en) | Synthetic fiber treatment composition | |
JP6631432B2 (en) | Film-forming silicone emulsion composition and fiber treating agent | |
JP4761396B2 (en) | Textile treatment agent | |
WO2022034829A1 (en) | Silicone emulsion composition and fiber treatment agent | |
JPH115905A (en) | Surface modifier composition | |
CN114846097A (en) | Water-proof absorbent and paper board | |
WO2024034400A1 (en) | Amino-modified silicone emulsion composition, method for manufacturing same, fiber treatment agent, and hair cosmetic | |
JPH09143885A (en) | Fiber treating agent composition | |
JPH0953016A (en) | Textile processing agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CROMPTON CORPORATION, CONNECTICUT Free format text: CHANGE OF NAME;ASSIGNOR:CK WITCO CORPORATION;REEL/FRAME:013299/0889 Effective date: 20000427 Owner name: CK WITCO CORPORATION, CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WITCO CORPORATION;REEL/FRAME:013243/0622 Effective date: 19990901 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |