US3144412A - Solid detergent compositions - Google Patents
Solid detergent compositions Download PDFInfo
- Publication number
- US3144412A US3144412A US66443A US6644360A US3144412A US 3144412 A US3144412 A US 3144412A US 66443 A US66443 A US 66443A US 6644360 A US6644360 A US 6644360A US 3144412 A US3144412 A US 3144412A
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- US
- United States
- Prior art keywords
- detergent
- weight
- water
- soil
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 86
- 239000013042 solid detergent Substances 0.000 title description 4
- 239000003599 detergent Substances 0.000 claims description 84
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000000375 suspending agent Substances 0.000 claims description 22
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 9
- 239000008240 homogeneous mixture Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 34
- 125000000217 alkyl group Chemical group 0.000 description 26
- -1 alkyl phenol Chemical compound 0.000 description 20
- 239000002002 slurry Substances 0.000 description 19
- 239000004615 ingredient Substances 0.000 description 16
- 229920002689 polyvinyl acetate Polymers 0.000 description 12
- 239000011118 polyvinyl acetate Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 241000219146 Gossypium Species 0.000 description 7
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 229940077388 benzenesulfonate Drugs 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- DUXXGJTXFHUORE-UHFFFAOYSA-M sodium;4-tridecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 DUXXGJTXFHUORE-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical group C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 2
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000005228 aryl sulfonate group Chemical group 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical class CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl 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])C([H])([H])[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- RQFVHGAXCJVPBZ-UHFFFAOYSA-N propylene pentamer Chemical compound CC=C.CC=C.CC=C.CC=C.CC=C RQFVHGAXCJVPBZ-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical class C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
Definitions
- the present invention relates to a detergent composition
- a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble non-ionic alkyl phenol polyalkylene oxide detergent, a water-soluble alkyl aryl sulfonate detergent, and a mixture of Water-soluble cellulosic and polyvinyl alcohol soil-suspending agents, as hereinafter described and claimed.
- compositions containing an organic detergent and a soil-suspending or anti-redeposition agent which inhibits the deposition of soil onto the fabric during the washing operation.
- the detergent content has included various anionic and non-ionic detergents including mixtures thereof.
- soilsuspending agents including natural and synthetic gums, cellulose derivatives such as carboxymethylcellulose, protein materials and various synthetic polymers including polyvinyl alcohol.
- the soil-suspending agent which has received Wide acceptance in the art has been sodium carboxymethylcellulose.
- the present invention relates to a detergent composition
- a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol polyalkylene oxide detergent and a water-soluble higher alkyl aryl sulfonate detergent in a ratio from about 90:10 to 30:70 by weight, and a minor proportion of a mixture of a water-soluble cellulosic soil-suspending agent and a water-soluble polyvinyl alcohol soil-suspending agent effective to enhance the soil-suspension properties thereof.
- a feature of this invention relates to a heat-treated composition in particulate form comprising about to 50% by weight of said mixture of non-ionic and sulfonate detergents with a mixture of carboxyalkylcellulose and polyvinyl alcohol suspending agents in amounts from 0.05 to 1% each by weight, and the balance being primarily water-soluble inorganic salts, preferably with 10 to 80% by weight of inorganic alkaline builder salts.
- Other features of the present invention will be apparent in the following description.
- compositions exhibit desirable detersive properties, particularly in soil-suspension effects during washing operations.
- a synergistic or enhanced improvement in soil-suspension is achieved by this combination as evideuced by a superior whiteness of washed fabrics such as cottons in the presence of carbonaceous soil compared to the effects achieved with an equivalent amount of said soil-suspending agents when employed individually.
- a high level of soil-suspension power is obtained with a Wide variety of fabrics in addition to cotton, including synthetic materials such as nylon, Dacron, resin-treated cottons and the like.
- the over-all effects are superior to the properties of compositions containing said detergents when employed individually and combinations thereof containing one of said soil-suspending agents.
- the water-soluble alkyl phenol alkylene oxide condensate detergents are known in the art.
- the degree or proportion of the hydrophilic alkyleneoxy groups present in a particular condensate will vary with the specific hydrophobic alkyl phenol group therein, generally increasing as the number of carbons in the hydrophobic group increases so as to be sufiicient to confer the desired watersolubility and detersive properties on the final product.
- the determination of a specific hydrophiliczhydrophobic relationship for each type is not the essential novelty of the 3,144,412 Patented Aug. 11,1964
- the condensates will possess at least about 5 and usually from 5 to 50 alkylene oxide groups.
- the number of ethenoxy groups per molecule of condensate may average about 7.5, 8.5, 9.5, 11.5, 20.5 or 30, with the preferred range being about 8 to 20 moles of ethylene oxide.
- the hydrophobic alkyl phenol portion has an alkyl group of at least about five, and usually about 8 to 20 carbons.
- the alkyl substituent or the aromatic nucleus may be diisobutylene, diamyl, iso-octyl, nonyl, ethyl hexyl, polymerized propylene, dimerized C -C olefin, and the like.
- the preferred alkyl substituents contain 8 to 12 carbons.
- the water-soluble higher alkyl aryl sulfonate detergents are known in the art and will usually have an average of about 8 to 15 carbon atoms in the alkyl group. It is preferred to use the higher alkyl benzene sulfonate detergent, though other similar detergents having a mononuclear aryl group, such as toluene, xylene or phenol may be used also.
- the higher alkyl substituent on the aromatic nucleus may be branched or straight chain in structure.
- branched-chain substituents are nonyl, dodecyl and pentadecyl groups derived from polymers of lower monoolefins including mixtures thereof and examples of straight chain alkyl groups are decyl, keryl and the like. It is preferred that the alkyl group has an average of 12-15 carbons.
- sulfonated detergents are used preferably in the form of their alkali metal salts such as the sodium and potassium salts.
- alkali metal salts such as the sodium and potassium salts.
- Other water-soluble salts such as the nitrogen-containing salts may be used also, examples being the ammonium, mono-, di-, and tri-ethanolamine salts, and isopropanolamine salts of said detergents.
- the water-soluble cellulosic soil-suspending agents are cellulose having a purity from about 60 to on a dry basis and which are of low, medium or high viscosity may be employed.
- the degree of substitution of the carboxymethyl group per anhydroglucose unit in the cellulose molecule is variable, but is Within the range from about 0.5 to 2, andusually up to 1.25 substitution. It is preferred to employ carboxylated cellulose having about 0.5 to 0.9 substitution, and particularly about 0.5 to 0.7.
- Other cellulosic salts are sodium carboxyethylcellulose, the cellulose sulfates and suitable lower alkyl and hydroxyalkyl ethers of cellulose.
- the soil-suspending agent used in admixture with the carboxyalkylcellulose or the like is Water-soluble polyvinyl alcohol.
- the specific or exact degree of polymerization is variable so that it may be of low, medium or high viscosity provided the material has the desired water-solubility and soil-suspending power to produce the enhanced effects in said mixtures.
- Suitable polyvinyl tains minor amounts of polyvinyl acetate such as up to about 30% by weight, and preferably from about to ester content.
- a suitable example is polyvinyl alcohol having a viscosity of 4 to 6 cps. with about 12% ester (88-89% hydrolysis).
- Other known polyvinyl alcohols are those with a viscosity of 21-25 cps. or 3545 cps. and about 12% ester.
- polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of about 10 to 30% by weight.
- This material exhibits maximum stability in heat-treatment of the composition resulting in maximum soil-suspending power for the composition. It may be prepared by any suitable manner such as by control of the degree of polymerization and alcoholysis of the polyvinyl acetate to produce a product of the above characteristics.
- the above viscosity range corresponds to an approximate weight average degree of polymerization of about to 100. Examples thereof are polyvinyl alcohols having a viscosity of 2.34 cps. and 22.3% polyvinyl acetate; 1.88 cps. and 19.6% ester; 1.98 cps. and 29.4% ester; 2.38 cps. and 12.8% ester; and the like.
- the non-ionic detergent and the alkyl aryl sulfonate detergent are employed in a ratio from about 90:10 to about 30:70 by weight, and preferably from 90:10 to :50. It has been found that maximum detersive effects are achieved in combination with the soil-suspending agents when employing the detergents within these ranges. There is achieved a synergistic increase in soil-suspension power of the composition in the washing of certain fabrics, and the over-all effects are superior to the use of the detergents individually.
- the mixture of detergents is important in the preparation of heat-treated solidified compositions.
- the heating of an aqueous slurry of an alkyl benzene sulfonate detergent with inorganic salts and a particular grade of polyvinyl alcohol (such as having a viscosity of 4-6 centipoises) in a crutcher for up to about one hour at an elevated temperature, e.g., 160180 F., followed by spray-drying results in a product having reduced soil-suspending power.
- this defect is due primarily to such factors as the nature of the polyvinyl alcohol in combination with said detergent in the aqueous slurry when it is subjected or aged at elevated temperatures prior to drying of the slurry to a solid composition.
- the presence of the alkyl phenol alkylene oxide detergent in said heated aqueous mixtures tends to stabilize the polyvinyl alcohol and insure that a high level of soilsuspension power is exhibited by the composition even after said heat-treatment.
- the maximum stabilizing effects are obtained where the detergent content is a major proportion of the non-ionic detergent and a minor proportion of the alkyl aryl sulfonate, the preferred ratios being from about :4O to 90:10 by weight.
- These detergents are present 1n any suitable amount in the composition and W111 be in an amount greater than the amount of the soilsuspendrng agents and usually at least about 5% by weight of total solids.
- the detergent content will be usually from about 5 to 50%, and preferably from 10 to 45% by weight.
- the amount of the combined soil-suspending agents is a minor proportion of the composition. While amounts of 0.05 to 5% by weight of each of the soil-suspending agents may be used if desired, it is a feature of the present invention to use a total amount of 0.1 to 2% by weight of the solids in a ratio from about 20:1 to 1:20 by weight, preferably within the range of about 10:1 to 1:10, of the cellulosic compound to polyvinyl alcohol and sufficient to exert the desired increase in soil-suspending power.
- the use of up to 2% of the soil-suspending agents has advantages in the manufacture of heat-dried compositions and particularly in soil-suspension effects.
- each soil-suspending agent so 4 that the total is not in excess of 2%, and preferably not in excess of 1.5% by weight of total solids. It is preferred that each agent be employed in an amount from about 0.05-1% and sufficient to achieve a high level of soil-suspension effects in the washing of both natural and synthetic fabrics.
- water-soluble inorganic salts there is present usually various amounts of watersoluble inorganic salts in the composition.
- Water-soluble neutral builder salts such as sodium sulfate may be present in admixture with the sulfonate detergent since such sulfate salts are formed in the manufacture of the alkyl aryl sulfonate by certain commercial methods. Additional amounts of such inorganic sulfates may be added as desired.
- a substantial amount of water-soluble alkaline inorganic builder salts such as about 10 to by weight of total solids, preferably 20 to 60%.
- These salts are preferably the alkali metal polyphosphate salts which have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavyduty performance of the detergent product. They may be considered as derived from orthophosphoric acid or the like by the removal of molecularly-bound water, though any suitable means of manufacture may be employed if desired.
- Such complex or molecularly dehydrated polyphosphate salts may be used in the form of the normal or completely neutralized salt, e.g., pentasodium tripolyphosphate, or partially neutralized salt, e.g., sodium acid tripolyphosphate.
- phosphate salts are pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate and the like including any desired mixtures thereof.
- alkaline builder salts may be employed also such as the water-soluble alkali metal silicates. These silicates may be employed as the sole builder salt if desired or in combination with the polyphosphates. Suitable silicates are those having an alkali oxide to silica ratio within the range of about 1:1 to 1:4, and preferably from about 1:2 to 1:3. Examples are sodium silicates having an Na O to SiO ratio of 1:2.35, 1:25, 1:32, 122.0, 121.6 and 1:1. Other materials are borax and sodium carbonate.
- the ingredients are to be admixed so as to form a substantially homogeneous product in solid form.
- Any suitable method may be employed including mechanical blending of the ingredients thoroughly to produce a uniform mixture.
- the preferred method comprises forming a fluid aqueous slurry containing the organic detergents in a conventional soap crutcher or any other suitable mixing apparatus such as a ribbon blender.
- the other ingredients are then added in any suitable order and form.
- the polyvinyl alcohol and cellulose compounds are added usually as fine white powders with stirring.
- the slurry should be sufiiciently fluid at elevated temperatures to insure adequate mixing and formation of a uniform product.
- the aqueous mixture is subjected to a heat-treatment at an elevated temperature such as within the range of about to 200 F., and usually from about to 180 F.
- the slurry is heated by external means or even by exothermic heat of reaction of certain ingredients when added to the slurry depending upon the desired temperature.
- the addition of hydratable inorganic salts such as the anhydrous forms of sodium tripolyphosphate and sodium pyrophosphate results in exothermic reactions as hydration occurs.
- the elevated temperature of the slurry aids in the mixing of the ingredients and in solubilization or hydration effects of specific ingredients in the slurry.
- the time interval of the mixing operation should be sufiicient to insure adequate mixing which will be usually at least a few minutes, e.g., 5 minutes.
- the aqueous mixture prior to drying is aged at the elevated temperature for a time sufiicient to insure adequate solubilization or hydration of certain ingredients.
- Such aging period may be for a number of hours, such as up to about 8 hours.
- time intervals of less than three hours prior to heat-drying, and preferably less than one hour. It is understood that excessively high temperatures or unduly long aging periods will be avoided to prevent decomposition and insure efficient processing.
- the solids content of the aqueous slurry is determined by the type of drying operation to be employed and will be usually within the range from about 20 to 90% total solids. In the manufacture of heat-dried products involving vaporization of the water, the solids content will be usually within the range of about 40 to 65% by weight, the remainder being substantially free water content. It is usually maintained at a temperature from about 160 to 180 F.
- the slurry may be subjected to any suitable heat-drying operation and converted to particle form. For example, the material from the crutcher or mixing vessel may be sent into a drop tank from where it may be added or pumped to a drying zone such as a spray tower.
- This mixture may be subjected to the conventional spraydrying, roll-drying or drum-drying operations utilizing temperatures above about 212 F. to produce the detergent composition in particulate form.
- the detergent composition is obtained in the form of heat-dried homogeneous particles, such as beads, granules, flakes, chips, powders, etc. 4
- composition is produced thereby in the form of hollow thin-walled spheres or beads, characterized by excellent solubility in water and uniformity of particles having a small residual moisture content usually of about 3 to by weight.
- the aqueous slurry may be solidified or dried by other suitable methods which do not involve vaporization of the water content.
- the slurry can contain sufficient water for adequate mixing and hydration of the hydratable inorganic salts to the extent desired Without any significant excess water content so that a dry and solidified mass is formed upon suitable aging at room temperature or slightly elevated temperatures such as up to about 120 F.
- the solidified mass may be granulated to form particles or granules of desired size.
- Various other materials may be added in known manner to the aqueous slurry or after solidification.
- higher fatty acid amides such as coconut or lauric monoethanolamide, isopropanolamide and diethanolamide
- fatty alcohols such as lauryl alcohol, coconut fatty alcohols or cetyl alcohol
- lower alkyl aryl sulfonates such as xylene or toluene sulfonates
- coloring agents corrosion inhibiting agents, bleaching agents, foam stabilizers or inhibitors as desired, detergency improving additives, and the like.
- suitable amounts of other detersive materials may be incorporated in the composition, such as suitable non-ionic and sulfated organic detergents.
- Examples thereof are the normal and secondary higher alkyl sulfate detergents, particularly those having 8 to 15 carbons in the alkyl residue such as lauryl (or coconut fatty alcohol) sulfate, the higher alkyl ether sulfates, higher alkyl glyceryl ether sulfonates, higher alkyl aryl polyethylene oxide sulfates, polyoxyethylene ethers of fatty alcohols, and polyethylene condensates with hydrophobic polypropylene glycols.
- lauryl or coconut fatty alcohol
- Example I A detergent composition is prepared according to the following formulation.
- the polyvinyl alcohol has a viscosity of 4-6 cps. and 11-12% polyvinyl acetate;
- the alkyl group of the sulfonate detergent is derived from a mixture containing propylene pentamer and tetramer benzene sulfonate corresponding on the average to a tridecyl group, and the carboxymethylcellulose is a commercial grade of about 67% purity, and the non-ionic detergent is nonyl phenol ethylene oxide having an average of about 9.5 moles ethylene oxide.
- This formulation is prepared in particulate form by mixing all of the solid ingredients except the non-ionic detergent and water in powdered form to form a homogeneous powder.
- the non-ionic detergent is a liquid and is slowly added with stirring followed by addition of the water and the composition gradually forms a dry granular mass which is passed through a 20 mesh screen (U.S. Sieve).
- the resulting product in particulate form is added to the washing machine and exhibits a high degree of washing power, particularly in soil-suspension power on cotton fabrics.
- Example 11 The formulation of Example I is repeated using polyvinyl alcohol of 2.34 centipoises and 22.3% polyvinyl acetate content. The resulting solid detergent composi-. tion exhibits high soil-suspension power also.
- Example III A solid detergent composition is prepared according to the following formulation.
- the non-ionic detergent is nonyl phenol condensed with an average of about 9.5 moles ethylene oxide
- the carboxymethylcellulose is a commercial grade (Du Pont 10D)
- the polyvinyl alcohol has a viscosity of 46 centipoises and 11-12% polyvinyl acetate.
- the composition is added to. a washing bath and exhibits superior washing properties on a variety of fabrics including cottons, Dacron-cotton mixtures, and resin-treated cottons. More particularly, this formulation has markedly superior soil-suspension properties on washing of cotton fabrics in soil anti-redeposition tests using carbon soil in soft water compared.
- Example IV A heat-dried composition is prepared according to the following formulation.
- the balance being small amounts of fluorescent dye, corrosion inhibitor and the like.
- the product is prepared by adding to a crutcher a 60% solids aqueous solution of the sulfonate detergent described in Example I admixed with some sodium sulfate formed in its manufacture.
- the non-ionic detergent having about 9.5 moles of ethylene oxide and the fatty alcohol are added as a liquid to the crutcher at 120 F.
- the tripolyphosphate in powder form is added with agitation and there is formed a smooth, pumpable mixture within a few minutes having a total solids content of about 55-60%. It is then pumped into a spray tower where it is spray-dried with air heated to about 600 F. to yield a product in the form of beads. The product exhibits high soil-suspension power in washing tests.
- a detergent composition comprising a substantially homogeneous mixture in solid form of (a) a water-soluble non-ionic higher alkyl phenol ethylene oxide detergent having about to 20 carbon atoms in the alkyl grou and about 5 to 50 mols of ethylene oxide and (b) a watersoluble higher alkyl mononuclear aryl sulfonate detergent having about 8 to carbon atoms in said alkyl group, the ratio of said non-ionic detergent to alkyl aryl sulfonate detergent being from about 90: 10 to 30:70 by weight and said detergents being in a total amount from about 5 to 50% by weight of the composition, and a mixture of (c) an alkali metal carboxymethylcellulose and (d) water-soluble polyvinyl alcohol soil-suspending agent having a viscosity within the range of about 1.8 to 65 centipoises, said carboxymethylcellulose and polyvinyl alcohol soil-suspending agents being from about 0.05 to 5% by weight of each in said
- a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate detergent having about 8 to 15 carbons in said alkyl group, the total amount of said non-ionic and said sulfonate detergents being from about 5 to 50% by weight of the composition in a ratio from about 90: 10 to :70 by weight, and in minor proportion to said detergents about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose soil-suspending agent and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts.
- a heateated detergent composition in particulate form comprising about 5 to 50% by weight of higher alkyl phenol ethylene oxide detergent having about 8 to 12 carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate having about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to about 6 centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts with about 10 to by weight of alkali metal phosphate.
- a spray-dried detergent composition in particulate form comprising about 5 to 50% of a mixture of watersoluble higher alkyl phenol ethylene oxide having 8 to 12 carbons in the alkyl group and about 8 to 20 moles of ethylene oxide and sodium higher alkyl benzene sulfonatc detergent having an average of about 12 to 15 carbons in said alkyl group in a ratio from about :10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of sodium carboxymethylcellulose and water-soluble polyvinyl alcohol in a ratio from about 20:1 to about 1:20 by weight, said polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, and the balance being primarily water-soluble inorganic builder salts.
- a process for preparing a substantially homogeneous detergent composition in solid form which comprises preparing an aqueous mixture having a solids content of about 20 to 90% by weight containing a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to 20 carbon atoms in the alkyl group and about 5 to 50 mols of ethylene oxide and a water-soluble higher alkyl mononuclcar aryl sulfonate detergent having about 8 to 15 carbons in said alkyl group in a ratio from about 90: 10 to 30:70 by weight, the total amount of said detergents being from about 5 to 50% by weight of solids, about 0.05 to 5% each by weight of solids of alkali metal carboxymethyl cellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to 65 centipoises in a ratio from about 20:1 to 1:20 by weight, the balance of total solids being primarily water-soluble inorganic builder salts, and forming
- a process for manufacturing a heat-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 20 to 90% by weight containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing about 5 to 20 carbon atoms in the alkyl group and 5-50 ethylene oxide groups and an alkali metal higher alkyl benzene sulfonate detergent having an average of about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by weight, alkali metal carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of from about 1.8 to 6 centipoises, the proportions on a solids basis being about 5 to 50% by Weight of said detergents, and 0.1 to 2% by weight of a mixture of the cellulose compound and polyvinyl alcohol in a ratio from about 20:1 to 1:20 by Weight, the balance of solids being primarily Water-soluble inorganic builder salts with about 10
- a process for manufacturing a spray-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 40 to 65% by Weight, containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing 8 to 12 carbons in the alkyl group and 8 to 20 moles of ethylene oxide and a sodium higher alkyl benzene sulfonate detergent having an average of about 12 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by Weight, sodium polyphosphate salt, sodium carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, the proportions of said ingredients on a solids basis being about 5 to by Weight of said detergents, 10 to by Weight of said polyphosphate and 0.05 to 1% each by Weight of the carboxymethylcellulose and polyvinyl alcohol, heating said mixture at a temperature from about
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA688539A CA688539A (en) | 1960-11-01 | Solid detergent compositions | |
NL270825D NL270825A (en(2012)) | 1960-11-01 | ||
GB931438D GB931438A (en(2012)) | 1960-11-01 | ||
BE609040D BE609040A (en(2012)) | 1960-11-01 | ||
US66443A US3144412A (en) | 1960-11-01 | 1960-11-01 | Solid detergent compositions |
DEC25157A DE1293378B (de) | 1960-11-01 | 1961-09-22 | Feste Wasch- und Reinigungsmittel |
CH1154461A CH414047A (de) | 1960-11-01 | 1961-10-04 | Wasch- oder Reinigungsmittel |
FR875438A FR1302897A (fr) | 1960-11-01 | 1961-10-09 | Composition détersive solide |
MY1966100A MY6600100A (en) | 1960-11-01 | 1966-12-31 | Solid detergent composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US66443A US3144412A (en) | 1960-11-01 | 1960-11-01 | Solid detergent compositions |
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US66443A Expired - Lifetime US3144412A (en) | 1960-11-01 | 1960-11-01 | Solid detergent compositions |
Country Status (8)
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US (1) | US3144412A (en(2012)) |
BE (1) | BE609040A (en(2012)) |
CA (1) | CA688539A (en(2012)) |
CH (1) | CH414047A (en(2012)) |
DE (1) | DE1293378B (en(2012)) |
GB (1) | GB931438A (en(2012)) |
MY (1) | MY6600100A (en(2012)) |
NL (1) | NL270825A (en(2012)) |
Cited By (24)
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---|---|---|---|---|
US3284364A (en) * | 1963-01-25 | 1966-11-08 | American Cyanamid Co | Soil anti-redeposition agents |
US3288859A (en) * | 1965-03-30 | 1966-11-29 | Procter & Gamble | Reactions of alkali metal salts of sulfinyl carbanions and alkanesulfenates with epoxy compounds and novel compounds derived therefrom |
US3325414A (en) * | 1963-10-01 | 1967-06-13 | Colgate Palmolive Co | Heavy duty detergent composition containing a quaternary ammonium salt |
US3350319A (en) * | 1966-01-18 | 1967-10-31 | Mo Och Domsjoe Ab | Aqueous detergent-inorganic builder concentrates |
US3959165A (en) * | 1972-09-15 | 1976-05-25 | Colgate-Palmolive Company | Biodegradable, non-polluting, heavy duty synthetic organic detergent composition |
US3970594A (en) * | 1975-03-18 | 1976-07-20 | The Procter & Gamble Company | Hard surface cleaning compositions |
US4020015A (en) * | 1971-10-12 | 1977-04-26 | Lever Brothers Company | Detergent compositions |
US4235735A (en) * | 1979-07-30 | 1980-11-25 | Milliken Research Corporation | Laundry detergent containing cellulose acetate anti-redeposition agent |
US4487710A (en) * | 1982-03-01 | 1984-12-11 | The Procter & Gamble Company | Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid |
WO2001007551A1 (de) * | 1999-07-26 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Verwendung von polyvinylalkoholen als schmutzablösevermögende waschmittelzusätze |
US6730722B1 (en) * | 1998-06-19 | 2004-05-04 | Wacker-Chemie Gmbh | Cross-linkable polymer powder compositions |
WO2004069973A1 (de) * | 2003-02-10 | 2004-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Verstärkung der reinigungsleistung von waschmitteln durch cellulosederivat und hygroskopisches polymer |
US20060030504A1 (en) * | 2003-02-10 | 2006-02-09 | Josef Penninger | Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties |
US20060035805A1 (en) * | 2003-02-10 | 2006-02-16 | Josef Penninger | Bleach-containing laundry detergent comprising cotton-active soil release-capable cellulose derivative |
US20060035804A1 (en) * | 2003-02-10 | 2006-02-16 | Josef Penninger | Use of cellulose derivatives as foam regulators |
US20060035801A1 (en) * | 2003-02-10 | 2006-02-16 | Josef Penninger | Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative |
US20060035806A1 (en) * | 2003-02-10 | 2006-02-16 | Josef Penninger | Increase in the water absorption capacity of textiles |
US20060046951A1 (en) * | 2003-02-10 | 2006-03-02 | Josef Penninger | Enhancement of the cleaning performance of laundry detergents by a combination of cellulose derivatives |
US20080196221A1 (en) * | 2007-02-15 | 2008-08-21 | Oscar Merlin Madrigal | Fastening device for securing flexible sheet material |
US20080234169A1 (en) * | 2007-03-20 | 2008-09-25 | Jean Pol Boutique | Detergent composition |
CN104459014A (zh) * | 2014-11-27 | 2015-03-25 | 华南理工大学 | 一种测定羧甲基纤维素钠取代度的方法 |
CN104458611A (zh) * | 2014-11-27 | 2015-03-25 | 华南理工大学 | 一种测定水溶性食品级羧甲基纤维素钠取代度的方法 |
CN104459013A (zh) * | 2014-11-27 | 2015-03-25 | 华南理工大学 | 一种低钠羧甲基纤维素钠的取代度测试方法 |
CN110913864A (zh) * | 2018-08-17 | 2020-03-24 | 邦泰生物工程(深圳)有限公司 | 一种稳定型烟酰胺核糖组合物及其制备方法 |
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GB1371101A (en) * | 1971-02-03 | 1974-10-23 | Unilever Ltd | Production of detergent compositions |
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- CA CA688539A patent/CA688539A/en not_active Expired
- BE BE609040D patent/BE609040A/xx unknown
- GB GB931438D patent/GB931438A/en active Active
- NL NL270825D patent/NL270825A/xx unknown
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- 1960-11-01 US US66443A patent/US3144412A/en not_active Expired - Lifetime
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1961
- 1961-09-22 DE DEC25157A patent/DE1293378B/de active Pending
- 1961-10-04 CH CH1154461A patent/CH414047A/de unknown
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US2874123A (en) * | 1954-09-07 | 1959-02-17 | Colgate Palmolive Co | Process for the preparation of granular compositions |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3284364A (en) * | 1963-01-25 | 1966-11-08 | American Cyanamid Co | Soil anti-redeposition agents |
US3325414A (en) * | 1963-10-01 | 1967-06-13 | Colgate Palmolive Co | Heavy duty detergent composition containing a quaternary ammonium salt |
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CN104459014A (zh) * | 2014-11-27 | 2015-03-25 | 华南理工大学 | 一种测定羧甲基纤维素钠取代度的方法 |
CN104458611A (zh) * | 2014-11-27 | 2015-03-25 | 华南理工大学 | 一种测定水溶性食品级羧甲基纤维素钠取代度的方法 |
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CN110913864A (zh) * | 2018-08-17 | 2020-03-24 | 邦泰生物工程(深圳)有限公司 | 一种稳定型烟酰胺核糖组合物及其制备方法 |
CN110913864B (zh) * | 2018-08-17 | 2022-12-13 | 邦泰生物工程(深圳)有限公司 | 一种稳定型烟酰胺核糖组合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
NL270825A (en(2012)) | |
BE609040A (en(2012)) | |
DE1293378B (de) | 1969-04-24 |
GB931438A (en(2012)) | |
MY6600100A (en) | 1966-12-31 |
CA688539A (en) | 1964-06-09 |
CH414047A (de) | 1966-05-31 |
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