CN1162531C - Process for forming cleaning composition - Google Patents
Process for forming cleaning composition Download PDFInfo
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- CN1162531C CN1162531C CNB988143283A CN98814328A CN1162531C CN 1162531 C CN1162531 C CN 1162531C CN B988143283 A CNB988143283 A CN B988143283A CN 98814328 A CN98814328 A CN 98814328A CN 1162531 C CN1162531 C CN 1162531C
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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims description 7
- 238000004140 cleaning Methods 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 94
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- 239000003599 detergent Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 82
- 239000000126 substance Substances 0.000 claims description 59
- 229920000768 polyamine Polymers 0.000 claims description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 230000004048 modification Effects 0.000 claims description 31
- 238000012986 modification Methods 0.000 claims description 31
- -1 N-oxide compound Chemical class 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 abstract 2
- 229920002873 Polyethylenimine Polymers 0.000 description 41
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 150000003141 primary amines Chemical class 0.000 description 13
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 150000003335 secondary amines Chemical class 0.000 description 9
- 150000003512 tertiary amines Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical group 0.000 description 4
- 238000012667 polymer degradation Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- PODAMDNJNMAKAZ-UHFFFAOYSA-N penta-2,3-diene Chemical group CC=C=CC PODAMDNJNMAKAZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 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
- 238000004061 bleaching Methods 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a method for preparing a detergent composition, which comprises steps as follows: at least one alkaline material and at least one active acid are supplied. The active acid and the alkaline material are added in a mixer. In the mixer, the active acid is basically neutralized to form a neutralized active detergent. At least one acid-sensitive polymer is added in the neutralized active detergent to form slurry, and the slurry is made into a detergent composition. The detergent composition formed by the method is also described in a text.
Description
Technical field
The present invention relates to a kind of preparation method of cleanser compositions and the cleanser compositions that forms by described method.Particularly, the present invention relates to contain the preparation method of cleanser compositions of polymkeric substance and the cleanser compositions that contains described polymkeric substance that forms by described method.
Background technology
Cleanser compositions particularly laundry detergent composition typically comprises the acidic substance that are present in the production process.For example, described production process can be used the anion surfactant of the active acid form that is neutralized in process of production.Though the tensio-active agent form that some anion surfactant can pre-neutralization is added, in some occasion, the tensio-active agent of this pre-neutralization can not with, quality is unreliable or expense is high.Therefore, typical production process adds active acid (acid active), and neutralization in process of production.
Usually add polymkeric substance in the cleanser compositions so that performances such as soil dispersion, antiredeposition, fabric-modifying to be provided.This polymkeric substance can be for example cooperates with dirt and remove dirt, trap dirt and reduce deposition again, combine with fabric soft feel(ing) is provided from clothing.
A base polymer that is specially adapted in the cleanser compositions is a modified polyamine polymers.This modified polyamine polymers typically provides one or more above-mentioned ideal performance.Particularly, this modified polyamine polymers can provide soil dispersion, antiredeposition and the fabric-modifying performance of for example improving.Described modified polyamine polymers can comprise for example additional link to each other with main polymer chain charged or charged group not.
The ideal performance of this polymkeric substance is typically relevant with the character of any chemical modification group that is attached thereto with its molecular weight.This polymkeric substance is modified polyamine polymers generally very expensive (comparing with other detergent ingredients) particularly, therefore uses with lower concentration.Yet above-mentioned performance is typically relevant with concentration, and the concentration of described polymkeric substance is high more, and required effect is big more.Therefore, wish to add the described polymkeric substance of effective concentration, but still keep the enough low preparation cost that does not consequently excessively increase described cleanser compositions of this concentration.
Therefore, the method that need under the situation that does not increase preparation cost, polymkeric substance be mixed cleanser compositions with the concentration that keeps polymer performance.
Summary of the invention
Have now found that the active acid that exists in the washing composition production process can make some polymer degradation, make it to split into the fragment of lower molecular weight, provide the validity of the polymer performance of wanting significantly to reduce.Herein this polymkeric substance is called in " acid-sensitive polymkeric substance ".Therefore, the present invention relates to a kind of improved preparation method who contains the cleanser compositions of active acid and acid-sensitive polymkeric substance, reduce the degraded of acid-sensitive polymkeric substance, thereby under the situation that does not increase preparation cost, keep polymer performance.
The present invention relates to a kind of preparation method of cleanser compositions, may further comprise the steps: at least a basic material and at least a active acid are provided, described active acid and described basic material are added in the mixing tank.Described active acid is neutralized in the formation and activated detergent basically in described mixing tank.With at least a acid-sensitive polymkeric substance add described in and form slip in the activated detergent, described slip is made cleanser compositions.The cleanser compositions that forms by aforesaid method is also described herein.
Read after the present invention and the appended claims, these and other feature of the present invention, aspect and advantage will be conspicuous to those skilled in the art.
The present invention is specifically related to following technical scheme:
1. the preparation method of a cleanser compositions, this method may further comprise the steps:
A., at least a basic material and at least a active acid are provided;
B. described active acid and described basic material are added in the mixing tank;
C. described active acid is neutralized in the formation and activated detergent basically in described mixing tank;
D. at least a acid-sensitive polymkeric substance is added described in and form slip in the activated detergent; With
E. described slip is made cleanser compositions,
Wherein said acid-sensitive polymkeric substance be included in by quaternized, replace or oxidation modification before corresponding to following formula:
Modified polyamine formula V is arranged
(n+1)W
mY
nThe polyamine main chain of Z or by quaternized, replace or oxidation modification before corresponding to following formula:
Modified polyamine formula V is arranged
(n-k+1)W
mY
nY '
kThe polyamine main chain of Z, wherein k is less than or equal to n, and described polyamine main chain had before modification greater than 200 daltonian molecular weight, wherein
I) the V unit is the terminal units of following formula:
Ii) the W unit is the backbone units of following formula:
Or
Or
Iii) the Y unit is the branching unit of following formula:
Iv) the Z unit is the terminal units of following formula:
Wherein main chain connection R unit is selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-, and composition thereof; R wherein
1Be C
2-C
6Alkylidene group and composition thereof; R
2For hydrogen ,-(R
1O)
xB and composition thereof; R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl, and composition thereof; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, and composition thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,
-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and composition thereof; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3, and composition thereof; Condition is when any E unit of nitrogen is hydrogen, and described nitrogen neither the N-oxide compound; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and composition thereof; M is sufficient hydrogen or the water-soluble cationic that satisfies charge balance; X is a water soluble anion; M has 4 to 400 value; N has 0 to 200 value; P has 1 to 6 value, and q has 0 to 6 value; R has 0 or 1 value; W has 0 or 1 value, and x has 1 to 100 value; Y has 0 to 100 value; Z has 0 or 1 value.
2. above 1 method also is included in the described slip of formation and makes described acid-sensitive polymer dispersed form the step of pre-composition in carrier before.
3. above 1 method also comprises the step of described slip spraying drying being made cleanser compositions.
4. above 1 method also is included in and forms described slip adds water glass before in described and in the activated detergent step.
5. above 1 method, wherein said basic material be selected from carbonate, phosphoric acid salt, silicate, layered silicate, oxyhydroxide, and composition thereof.
6. above 2 method, wherein the weight ratio of carrier and acid-sensitive polymkeric substance is at least 1: 1.
7. above 2 method, wherein said carrier comprises water.
According to the present invention, have now found that cleanser compositions can use active acid and acid-sensitive polymkeric substance, and avoid acid to cause acid-sensitive polymer degradation.Owing to not needing the degraded for compensation expection to add extra acid-sensitive polymkeric substance, thereby this improves one's methods keep polymer properties and benefit under the situation that does not increase preparation cost.This improves one's methods and reduces degraded, therefore the validity of the acid-sensitive polymkeric substance of specified rate is improved.
Except as otherwise noted, herein all percentage, ratio and ratio all based on the weight of final cleanser compositions.Except as otherwise noted, all temperature all with degree centigrade (℃) expression.All documents of quoting all are incorporated herein for reference.
Term used herein " alkyl " means straight chain or branching, saturated or undersaturated hydrocarbyl portion.Except as otherwise noted, moieties is preferably saturated or the undersaturated of two keys is arranged, and preferably has one or two two key.The moieties that comprises acyl group in the term " alkyl ".
The active acid that term used herein " neutralization basically " means at least 50%, preferably at least 80%, more preferably at least 85% (weight) is neutralized.
According to the present invention, have realized that the active acid that exists in the typical cleanser compositions production process can make some polymer degradation, makes it to split into the fragment of the significantly reduced lower molecular weight of validity.Therefore herein this polymkeric substance is called in " acid-sensitive polymkeric substance ".Do not think bound by theory, believe that active acid can make it to degrade or otherwise loses its validity in sanitising agent with acid-sensitive polymer reaction.For example, active acid can reduce the performance of acid-sensitive polymkeric substance in cleanser compositions with the reaction of active group on the acid-sensitive polymkeric substance.In another example, it is significantly reduced than small segment that active acid can be reacted the validity that make it hydrolysis and split in cleanser compositions with the main chain of acid-sensitive polymkeric substance.
The inventive method also reduces the polymerization of undesirable acid-sensitive polymkeric substance.Do not think bound by theory, believe when some acid-sensitive polymkeric substance runs into acid undesirably to form homopolymer or multipolymer.This undesirable polymerization may destroy or reduce validity and the performance of described polymkeric substance in final composition.
Therefore, the inventive method reduces this type of undesirable reaction by the described active acid that neutralized basically before adding acid-sensitive polymkeric substance.In addition, this improves one's methods other benefit also is provided.For example,, need add less acid-sensitive polymkeric substance, thereby reduce preparation cost for identical beneficial effect the present invention is provided because described acid-sensitive polymkeric substance is generally very expensive.Otherwise because the beneficial effect of described acid-sensitive polymkeric substance is general relevant with its concentration in cleanser compositions, so the inventive method improves total effectiveness of the acid-sensitive polymkeric substance of specified rate.
In the inventive method, provide at least a basic material described active acid that is used to neutralize.Described basic material can be to be applicable to particularly any basic material of laundry detergent composition of cleanser compositions.Described basic material typically is selected from basic metal and alkaline earth salt, for example their carbonate, phosphoric acid salt, silicate, layered silicate, oxyhydroxide, and composition thereof.
The preferred example that is applicable to carbonate of the present invention comprises supercarbonate and sesquicarbonate, more preferably yellow soda ash (being SODA ASH LIGHT 99.2), salt of wormwood, and composition thereof.
If allow, basic metal and alkali earth metal phosphate are specially adapted to the present invention, because they can play the dual purpose of basic material and washing assistant.If present, described washing assistant can assist to control hardness of minerals and remove granular dirt.Be applicable to that preferably phosphate of the present invention includes but not limited to polyphosphoric acid (for example tripolyphosphate, tetra-sodium and glassy poly-metaphosphoric acid), phosphonic basic metal, ammonium and alkanol ammonium salts and composition thereof.
Basic metal and alkaline earth metal silicate and layered silicate also are applicable to the present invention.The example of silicate-like builder is an alkalimetal silicate, particularly SiO
2: Na
2O was than those and layered silicate in 1.6: 1 to 3.2: 1 scopes, authorized lamina sodium silicate described in the US4664 839 of Rieck as on May 12nd, 1987.NaSKS-6 is the trade mark (often being abbreviated as " SKS-6 " herein) of the crystalline layered silicate of Hoechst sale.NaSKS-6 has δ-Na
2SiO
5The layered silicate of form.SKS-6 is preferred for layered silicate of the present invention very much, but other this type of layered silicate also is applicable to the present invention: NaMSi if any those of following general formula
xO
2x+1YH
2O, wherein M is sodium or hydrogen, and x is 1.9 to 4 a number, preferred 2, and y is 0 to 20 number, preferred 0.Various other layered silicates from Hoechst comprise NaSKS-5, NaSKS-7 and NaSKS-11, are α, β and γ form.As mentioned above, most preferably be used for the δ of being of the present invention-Na
2SiO
5(NaSKS-6 type).Other silicate may also be suitable for, and Magnesium Silicate q-agent for example can be used as the component of curl (crispening) agent, oxygen bleaching stablizer and foam control system in the granular preparation.
Be applicable to that oxyhydroxide of the present invention is preferably sodium hydroxide, as be used for the alkali N-process.Typically, the aqueous solution with caustic sodium hydroxide adds in the mixing tank, with the described active acid that neutralizes.
Be applicable to that basic material of the present invention typically infeeds in the described cleanser compositions with the stoichiometry mol ratio of the described active acid that is enough at least to neutralize fully.Typically, described basic material surpasses stoichiometry.The stoichiometry mol ratio of basic material and active acid is at least 1: 1, preferably at least 1.2: 1.In some method such as agglomeration method, the stoichiometry mol ratio of this basic material and active acid can reach 8: 1 or be more.
The inventive method also provides and adds in the mixing tank by at least a active acid of described basic material neutral.Be applicable to that active acid of the present invention typically is the anion surfactant of sour form.
Be applicable to that anion surfactant of the present invention typically comprises the sulfonated surfactants and the sulfonation surface active material of sour form.Being specially adapted to of the present invention is the conventional C of sour form
11-C
18Alkylbenzene sulfonate.This alkylbenzene sulfonate can be alkylsulfonate, linear alkyl benzene sulfonate (" LAS ") or its mixture of branching.The anion surfactant of wanting of sulfuric acid and/or sulphonic form typically, is provided.For example,, can provide the linear alkyl Phenylsulfonic acid in final cleanser compositions, then by the inventive method neutralization for the linear alkyl benzene sulfonate is provided.
The inventive method may further comprise the steps: active acid and basic material are added in the mixing tank.Described active acid is neutralized in the formation and activated detergent basically in described mixing tank.Be applicable to that mixer types of the present invention comprises the liquid mixer of commercially available intermittent type slip mixing tank (being also referred to as " crutcher ") or any kind.But these mixing tank operate continuouslys are for example in multistep processes.Operation described herein can be finished in single mixing tank or a plurality of mixing tank as required.
The content that is applicable to described active acid of the present invention typically be final cleanser compositions weight about 10 to about 65%, preferred about 12 to about 45%, more preferably from about 15 to about 35% (weight).
In the preferred embodiment of methods described herein, before adding acid-sensitive polymkeric substance, in described He in the activated detergent, add water glass.Do not think bound by theory, believe and guarantee alkaline environment like this, thereby prevent that further any residual active acid from making acid-sensitive polymer degradation.
The present invention also provides acid-sensitive polymkeric substance.Be applicable to that the reaction of acid-sensitive polymkeric substance of the present invention and active acid descends the validity of described acid-sensitive polymkeric substance in cleanser compositions.As previously described, descend may be because of due to the chemically changed of the active group of for example acid-sensitive polymkeric substance, acid-sensitive main polymer chain actual cracked etc. for this validity.Be preferred for acid-sensitive polymkeric substance of the present invention comprise soil dispersion polymkeric substance, antiredeposition polymkeric substance and fabric-conditioning polymkeric substance, and composition thereof.More preferably be used for multipolymer that polymer type of the present invention comprises modified polyamine polymers, polyacrylate polymers, vinylformic acid and toxilic acid, and composition thereof.
Modified polyamine polymers particularly preferably among the present invention as acid-sensitive polymkeric substance.These polymkeric substance add fashionable very easily acid with active acid and cause degraded in normal agglomeration process.These modified polyamine polymers even more preferably comprise modified polyethyleneimine polymers linear or the ring-type main chain.Described polyamine main chain also can comprise the polyamine side chain more or less.Usually, polyamine main chain described herein by this way modification so that hereinafter by be substituted, the unit of quaternized, oxidation or its combination describes each nitrogen of described polyamine chain.
Term among the present invention " modification " is defined as with the hydrogen atom (replacement) of E unit replacement main chain-NH, makes main chain nitrogen quaternized (quaternized) or make main chain nitrogen be oxidized to N-oxide compound (oxidation).When meaning the process of the hydrogen atom that links to each other with main chain nitrogen with the replacement of E unit, term " modification " and " replacement " are used interchangeably.Quaternized or oxidation can not have under the situation about replacing at some sometimes and take place, but replaces preferably with the oxidation of at least one main chain nitrogen or quaternized.
Linear or the non-annularity polyamine main chain that constitutes modified polyethyleneimine polymers of the present invention has following general formula:
Described main chain before follow-up modification, comprise by R " connection " unit link to each other primary, the second month in a season and tertiary amine nitrogen.The cyclic polyamines main chain that constitutes modified polyethyleneimine polymers of the present invention has following general formula:
Described main chain before follow-up modification, comprise by R " connection " unit link to each other primary, the second month in a season and tertiary amine nitrogen.
Be defined as V or Z " end " unit after the primary amine nitrogen of described main chain of formation or side chain is modified among the present invention.For example, be positioned at the primary amine part that a described polyamine main chain or a chain end have following structure:
H
2N-R]-
By after the modification of the present invention, be defined as V " end " unit, or abbreviate the V unit as.Yet for the present invention, some or all described primary amine partly stand restriction that this paper further describes later may be still unmodified.These unmodified primary amine parts still are " end " unit because of its position in main chain.Similarly, be positioned at the primary amine part that described polyamine main chain end has following structure:
-NH
2
By after the modification of the present invention, be defined as Z " end " unit, or abbreviate the Z unit as.This unit stands restriction that this paper further describes later may be still unmodified.
Similarly, be defined as W " main chain " unit after the secondary amine nitrogen that constitutes described main chain or side chain is modified.The secondary amine part (chief component of main chain of the present invention and side chain) that following structure for example, is arranged:
By after the modification of the present invention, be defined as W " main chain " unit, or abbreviate the W unit as.Yet for the present invention, some or all described secondary amine parts may be still unmodified.These unmodified secondary amine parts still are " main chain " unit because of its position in main chain.
Similarly, be called Y " branching " unit after the tertiary amine nitrogen that constitutes described main chain or side chain is modified.The tertiary amine part (it is the chain component point of polyamine main chain or other side chain or ring, and wherein B represents the continuity of branched chain structure) that following structure for example, is arranged:
By after the modification of the present invention, be called Y " branching " unit, or abbreviate the Y unit as.Yet for the present invention, some or all described tertiary amine parts may be still unmodified.These unmodified tertiary amine parts still are " branching " unit because of its position in main chain.The R unit that accompanies with V, W and Y unit that is used to connect described polyamine nitrogen is described in the back.
Therefore, the final modified structure of modified polyethyleneimine polymers of the present invention can be represented by following general formula for linear modified polyethyleneimine polymers:
V
(n+1)W
mY
nZ
Can represent by following general formula for the ring-type modified polyethyleneimine polymers:
V
(n-k+1)W
mY
nY’
kZ
Comprise at modified polyethyleneimine polymers under the situation of ring, use the tapping point of the Y ' unit of following formula as main chain or supporting ring:
For each Y ' unit, have the Y unit of following formula will form the tie point of described ring to described main polymer chain or side chain:
Described main chain be the domain in particular cases, described polyamine main chain has following formula:
Thereby do not contain the Z terminal units, following formula is arranged:
V
n-kW
mY
nY’
k
Wherein k is for forming the branching unit number of ring.Preferred polyamine main chain of the present invention does not contain ring.
Under the situation of non-annularity modified polyethyleneimine polymers, index n is meant the relative degree of branching with the ratio of exponent m.The present invention's nonbranched linear modified polyethyleneimine polymers fully has following formula:
VW
mZ
Be that n equals 0.N value big more (m is more little with the ratio of n), the degree of branching in the molecule is high more.Typically to about 400 scope, bigger m value also is preferred to the value of m in minimum value 4, and particularly the value of index n is minimum or near 0 o'clock.
Each polyamine nitrogen is no matter be primary, the second month in a season or uncle's nitrogen all is further defined as one of following three classes after by modification of the present invention: simply replace, quaternized or oxidation.Unmodified those polyamine nitrogen unit according to they be primary, the second month in a season or uncle's nitrogen is divided into V, W, Y or Z unit.Promptly for the present invention, unmodified primary amine nitrogen is V or Z unit, and unmodified secondary amine nitrogen is the W unit, and unmodified tertiary amine nitrogen is the Y unit.
The primary amine of modification partly is defined as V " end " unit, and it has one of following three kinds of forms:
A) the simple replacement unit of following structure is arranged:
B) the quaternized unit of following structure is arranged:
Wherein X is the suitable counter ion that make charge balance; With
C) oxidation unit of following structure is arranged:
The secondary amine of modification partly is defined as W " main chain " unit, and one of following three kinds of forms are arranged:
A) the simple replacement unit of following structure is arranged:
B) the quaternized unit of following structure is arranged:
Wherein X is the suitable counter ion that make charge balance; With
C) oxidation unit of following structure is arranged:
The tertiary amine of modification partly is defined as Y " branching " unit, and one of following three kinds of forms are arranged:
A) the unmodified unit of following structure is arranged:
B) the quaternized unit of following structure is arranged:
Wherein X is the suitable counter ion that make charge balance; With
C) oxidation unit of following structure is arranged:
Some modification primary amine partly is defined as Z " end " unit, and one of following three kinds of forms are arranged:
A) the simple replacement unit of following structure is arranged:
B) the quaternized unit of following structure is arranged:
Wherein X is the suitable counter ion that make charge balance; With
C) oxidation unit of following structure is arranged:
Any position does not replace or when unmodified, is interpreted as with hydrogen to replace E on the nitrogen.For example, the unitary primary amine of the E unit that comprises a hydroxyethyl form is the V terminal units that following formula is arranged:
(HOCH
2CH
2)HN-。
For the present invention, two class chain end unit V and Z unit are arranged.Described Z " end " unit is by structure-NH
2The amino part of terminal primary derive.Non-annularity polyamine main chain of the present invention only comprises a Z unit, and cyclic polyamines may not contain the Z unit.Any E unit that described Z " end " unit can be further described later replaces, when described Z unit is modified into the N-oxide compound except.Nitrogen is oxidized under the situation of N-oxide compound in described Z unit, and described nitrogen must be modified, thereby E can not be hydrogen.
Modified polyethyleneimine polymers of the present invention comprises main chain R " connection " unit that is used to connect the main chain nitrogen-atoms.The R unit comprises among the present invention and is called " alkyl R " unit and " containing oxygen R " unitary those unit.Described " alkyl " R unit is C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene (wherein said hydroxylic moiety can be positioned at any position of described R cellular chain, except that described carbon atom directly with described polyamine main chain nitrogen links to each other), C
4-C
12Alkyl sub-dihydroxy (wherein said hydroxylic moiety can account for any two carbon atoms of described R cellular chain, except that those carbon atoms directly with described polyamine main chain nitrogen links to each other), C
8-C
12Dialkyl group arylidene (being that the arylidene part of two alkyl substituents as the connection chain part arranged for the present invention).For example, the dialkyl group arylene units has following formula:
Or
But described unit needn't be 1, and 4-replaces, and also can be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and composition thereof, more preferably ethylidene.Described " containing oxygen ", the R unit comprised-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-,-(R
1O)
xR
1-, and composition thereof.Preferred R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-, preferred R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OH) CH
2)
w-, and composition thereof, even preferred R unit is C
2-C
12Alkylidene group, C
3Hydroxy alkylidene, and composition thereof, C most preferably
2-C
6Alkylidene group.The most preferred main chain of the present invention comprises at least 50% ethylidene R unit.
R
1The unit is C
2-C
6Alkylidene group, and composition thereof, preferred ethylidene.R
2For hydrogen and-(R
1O)
xB, preferred hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl, and composition thereof, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the unitary part of the described E in back.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
10Alkylidene group, C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group, most preferably ethylidene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-C (O) (R
4)
rC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-, R
5Be preferably ethylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O) yR
1OCH
2CH (OH) CH
2-, more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
R is further pressed in described preferred " containing oxygen " R unit
1, R
2And R
5The unit definition.The R unit comprises preferred R preferably " to contain oxygen "
1, R
2And R
5The unit.The preferred modified polyethyleneimine polymers of the present invention comprises at least 50% ethylidene R
1The unit.Preferred R
1, R
2And R
5The unit combines with described " containing oxygen " R unit in the following manner and produces preferred " containing oxygen " R unit:
I) with preferred R
5Substitution-(CH
2CH
2O)
xR
5(OCH
2CH
2)
x-generation-(CH
2CH
2O)
xCH
2CHOHCH
2(OCH
2CH
2)
x-.
Ii) with preferred R
1And R
2Substitution-(CH
2CH (OR
2) CH
2O)
z-(R
1O)
yR
1O (CH
2CH (OR
2) CH
2)
w-generation-(CH
2CH (OH) CH
2O)
z-(CH
2CH
2O)
yCH
2CH
2O (CH
2CH (OH) CH
2)
w-.
Iii) with preferred R
2Substitution-CH
2CH (OR
2) CH
2-generation-CH
2CH (OH) CH
2-.
The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
mB ,-C (O) R
3, preferred hydrogen, C
2-C
22Hydroxy alkylidene, benzyl, C
1-C
22Alkylidene group ,-(R
1O)
mB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, most preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3Unmodified or when replacing, hydrogen atom is still as the part of representing E on the nitrogen.
Described V, W or Z unit are oxidized to be described nitrogen when being the N-oxide compound, and the E unit is hydrogen atoms not.For example, described main chain or side chain do not contain the unit of following structure:
Or
Or
In addition, described V, W or Z unit are oxidized to be described nitrogen when being the N-oxide compound, and the E unit does not comprise directly and the carbonyl moiety of nitrogen atom bonding.According to the present invention, described E unit-C (O) R
3Part not with the nitrogen bonding of N-oxide modifying, promptly do not have N monoxide acid amides or its composition of following structure:
Or
Or
B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSOxM) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, preferred hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M, more preferably hydrogen or-(CH
2)
qSO
3M.
M is sufficient hydrogen or the water-soluble cationic that satisfies charge balance.For example, sodium cation satisfies-(CH equally
2)
pCO
2M and-(CH
2)
qSO
3M, and form-(CH
2)
pCO
2Na and-(CH
2)
qSO
3The Na part.Capable of being combined more than a univalent cation (sodium, potassium etc.) to satisfy desired chemical charge balance.Yet, can be more than an anion-radicals by a divalent cation charge balance, perhaps for the electric charge needs that satisfy the polyanionic group may needs more than a univalent cation.For example, by sodium atom replace-(CH
2)
pPO
3M partly has following formula :-(CH
2)
pPO
3Na
3Divalent cation such as calcium (Ca
2+) or magnesium (Mg
2+) can replace other monovalence water-soluble cationic that is fit to or combination with it.Preferred cation is sodium and potassium, more preferably sodium.
X is water soluble anion such as chlorion (Cl
-), bromide anion (Br
-) and iodide ion (I
-) or X can be any electronegative group such as sulfate radical (SO
4 2-) and first thiosulfuric acid negatively charged ion (CH
3SO
3 -).
Index has following value: p that 1 to 6 value is arranged in the formula, and q has 0 to 6 value; R has 0 or 1 value; W has 0 or 1 value, and x has 1 to 100 value; Y has 0 to 100 value; Z has 0 or 1 value; M has 4 to about 400 value, and n has 0 to about 200 value; M+n has at least 5 value.
The preferred modified polyethyleneimine polymers of the present invention comprises such polyamine main chain, wherein is less than about 50% R base and comprises " containing oxygen " R unit, preferably be less than about 20%, more preferably less than 5%, most preferably described R unit does not comprise " containing oxygen " R unit.
The most preferred unitary modified polyethyleneimine polymers of " containing oxygen " R that do not comprise comprises such polyamine main chain, wherein is less than 50% R base and contains more than 3 carbon atoms.For example, ethylidene, propylene and trimethylene contain 3 or carbon atom still less, are preferred " alkyl " R unit.Be that main chain R unit is C
2-C
12Alkylidene group, preferred C
2-C
3Alkylidene group, most preferably ethylidene.
Modified polyethyleneimine polymers of the present invention comprises all even non-homogeneous polyamine main chain of modification, wherein 100% or still less-the NH unit is modified.Term among the present invention " evenly polyamine main chain " is defined as the polyamine main chain of identical R unit (promptly complete is ethylidene).Yet other the external unitary polyamine that comprises because of the described main polymer chain of formation of the artificial existence of selected chemical synthesis process is not got rid of in the definition of this homogeny.For example, those skilled in the art will know that thanomin can be as " initiator " in polymine synthetic, thereby comprise one and be considered to comprise the even polyamine main chain of the present invention because of hydroxyethyl polymine sample partly due to " initiator " polymerization.Comprising and not having the unitary polyamine main chain of the unitary full ethylidene R of branching Y is even main chain.Regardless of the ring-type side chain number of the degree of branching or existence, comprise the unitary polyamine main chain of full ethylidene R and be even main chain.
Term among the present invention " non-homogeneous main polymer chain " means the complex body that the polyamine main chain is different R element lengths and R cell type.For example, non-homogeneous main chain comprises ethylidene and the unitary mixing of propylene R unit.For the present invention, provide non-homogeneous main chain to need not to be the unitary mixture of " alkyl " and " containing oxygen " R.Suitably control these " R unit chain lengths " makes formulator can change the solubleness and the fabric solidness of modified polyethyleneimine polymers of the present invention.
The preferred modified polyethyleneimine polymers of the present invention comprises so even polyamine main chain, they all or part of by polyoxyethylene partly replace, for all or part of quaternised amine, all or part of N-of the being oxidized to oxide compound of nitrogen, and composition thereof.Yet, the modification in the same manner of not all main chain amine nitrogen, the makers-up can select modification as required.Ethoxylation degree is also determined by makers-up's real needs.
The preferred polyamine that constitutes the The compounds of this invention main chain is generally polyalkylene amine (PAA ' s), polyalkyleneimine (PAI ' s), preferably polyethylene amine (PEA ' s), polymine (PEI ' s) or by PEA ' s or the PEI ' s that connects than the unitary part of parent PAA ' s, PAI ' s, PEA ' s or the longer R of PEI ' s arranged.Polyalkylene amine (PAA) commonly used is four butylidenes, five amine.PEA ' s is by the reaction of ammonia and ethylene dichloride, fractionation obtains then.Common PEA ' the s of gained is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).Be hexamine, seven amine, eight amine and nine possible amine more than five amine, as if general symbiotic mixture can not pass through fractionation by distillation, may comprise other material such as cyclammonium, particularly piperazines.May also have the cyclammonium of the side chain that nitrogen-atoms wherein occurs.US2 792372 referring to authorizing Dickinson May 14 nineteen fifty-seven has wherein described the preparation of PEA ' s.
Preferred amine polymer main chain is included as C
2The unitary R of alkylidene group (ethylidene) unit is also referred to as polymine (PEI ' s).Preferred PEI ' s has medium at least branching, and promptly m is lower than 4: 1 with the ratio of n, but most preferably the ratio of m and n is about 2: 1 PEI ' s.Preferred main chain had following general formula before modification:
Wherein m is identical with the definition of front with n.Preferred PEI ' s had before modification greater than about 200 daltonian molecular weight.
In the described polyamine main chain (particularly under the situation of PEI ' s) primary, the second month in a season and the unitary relative proportion of tertiary amine will change according to preparation method.Each hydrogen atom representative that links to each other with each nitrogen-atoms of described polyamine main chain is used for the potential site of follow-up replacement, quaternized or oxidation.
These modified polyethyleneimine polymers can by for example in the presence of catalyzer such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc. the polymerising ethylene imines prepare.The concrete grammar for preparing these polyamine main chains is disclosed in the US2 182 306 that authorizes December 5 nineteen thirty-nine such as Ulrich etc.; Authorized the US3 033 746 of Mayle etc. on May 8th, 1962; Authorized the US2 208 095 of Esselmann etc. on July 16th, 1940; Authorize the US2 806 839 of Crowther September 17 nineteen fifty-seven; Authorize among the US2 553 696 of Wilson with May 21 nineteen fifty-one, all documents all are incorporated herein for reference.
Formula I-IV explanation comprises the example of the modified polyethyleneimine polymers of the present invention of PEI ' s:
Formula I illustrates the modified polyethyleneimine polymers that comprises the PEI main chain, and wherein all commutable nitrogen are all by using polyoxy alkylidene oxygen base (polyoxyalkyleneoxy) unit-(CH
2CH
2O)
7H replaces the hydrogen modification, and it has following formula:
Formula I
This is all by an example of one type partially modified modified polyethyleneimine polymers.
Formula II illustrates the modified polyethyleneimine polymers that comprises the PEI main chain, and wherein all commutable primary amine nitrogen are all by using polyoxy alkylidene oxygen base unit-(CH
2CH
2O)
7H replaces the hydrogen modification, makes all oxidable primary and secondary nitrogen all be oxidized to the N-oxide compound then and makes described molecule modification, and described modified polyethyleneimine polymers has following formula:
Formula II
Formula III illustrates the modified polyethyleneimine polymers that comprises the PEI main chain, and wherein all main chain hydrogen atoms all are substituted, and some main chain amine units are quaternized.Described substituting group is polyoxy alkylidene oxygen base unit-(CH
2CH
2O)
7H or methyl.Described modified PE I soil release polymers has following formula:
Formula III
Formula IV illustrates the modified polyethyleneimine polymers that comprises the PEI main chain, and wherein said main chain nitrogen is by replacing (i.e. quilt-(CH
2CH
2O)
7H or methyl substituted), quaternized, be oxidized to N-oxide compound or its combination modification.The gained modified polyethyleneimine polymers has following formula:
Formula IV
In the above example, not that unitary all nitrogen of a class all comprise identical modification.The present invention allows the makers-up to make the ethoxylation of a part of secondary amine nitrogen and makes other secondary amine nitrogen be oxidized to the N-oxide compound.This also is applicable to primary amine nitrogen, promptly the makers-up can be selected in oxidation or quaternized before make the modification of all or part of primary amine nitrogen with one or more substituting group.Except that restriction noted earlier, desirable what possible E base of acting as makes up on primary and secondary amine nitrogen.
The content that is applicable to acid-sensitive polymkeric substance of the present invention typically be described cleanser compositions weight about 0.05 to about 15%, preferred about 0.1 to about 10%, more preferably from about 0.2 to about 7% (weight).If acid-sensitive polymkeric substance of the present invention is a modified polyethyleneimine polymers, then its content typically be described cleanser compositions weight about 0.05 to about 2%, preferred about 0.1 to about 1%, more preferably from about 0.2 to about 0.8% (weight).
In the present invention's one preferred embodiment, a kind of carrier is provided, acid-sensitive polymer dispersed forms pre-composition in carrier.Because described acid-sensitive polymkeric substance typically is solid or mucus, and typically uses described acid-sensitive polymkeric substance with lower concentration, institute think make acid-sensitive polymkeric substance be evenly dispersed in and in the activated detergent, need carrier usually.Described carrier typically is liquid, can only be used as carrier, perhaps can rise difunctional.Owing to will make acid-sensitive polymer dispersed in wherein forming pre-composition, described carrier is preferably non-acid as water.Nonaqueous carrier or basic supports also are applicable to the present invention.
Must provide the carrier of capacity so that acid-sensitive polymkeric substance is easy to disperse (preferred dissolution) in wherein forming pre-composition.The weight ratio of carrier and acid-sensitive polymkeric substance typically is at least about 1: 1 in the described pre-composition, preferred about 1: 1 to about 8: 1.
During acid-sensitive polymkeric substance or the pre-composition that will contain acid-sensitive polymkeric substance in preferred embodiments added and form slip in the activated detergent.This is typically at mixing tank or make in the device of slip homogenizing and carry out.Described mixing tank can be the same mixing tank that uses in the neutralization procedure of front, or different mixing tanks.By for example spraying drying or agglomeration method known in the art described slip is made cleanser compositions then.
In a preferred method, in the conventional spray-drying tower of under about 180 temperature ins to about 450 ℃ of scopes, operating described slip is made spray-dried granules.The operation of this known device sprays into described slip in adverse current (or and stream) hot blast by nozzle and makes the slip drying, forms the porous spray-dried granules at last.
Embodiment
Providing embodiments of the invention below is used for illustrating and not limiting the present invention in any way.
Embodiment 1
Prepare cleanser compositions by the following method.About 20-25% is provided the active acid corresponding to the LAS of sour form.The caustic hydroxide dilute solution that about 1.2 times of stoichiometric requirement amounts are provided is with the described active acid that neutralizes.Described active acid and basic material are added in the mixing tank, during neutralization forms therein and activated detergent.With about 8% silicate add described in and in the activated detergent.Acid-sensitive polymkeric substance (modified polyethyleneimine polymers has the main chain of MW1800, and ethoxylation degree is about 7) is provided, mixed forming pre-composition with about 1: 1 to about 8: 1 weight ratio with water.Then described pre-composition is added in the described mixing tank, mix forming slip in about 10 seconds.Other detergent ingredients such as phosphoric acid salt, vitriol etc. also add at this moment.
Then described slip is poured in the dropping liquid tank, pumping is made spray-dried granules by the pressurized nozzles in the spray tower under the pressure of 40-70bar.Described spray tower adopts counter-flow air stream, and temperature in is about 320-350 ℃.
Claims (7)
1. the preparation method of a cleanser compositions, this method may further comprise the steps:
A., at least a basic material and at least a active acid are provided;
B. described active acid and described basic material are added in the mixing tank;
C. described active acid is neutralized in the formation and activated detergent basically in described mixing tank;
D. at least a acid-sensitive polymkeric substance is added described in and form slip in the activated detergent; With
E. described slip is made cleanser compositions,
Wherein said acid-sensitive polymkeric substance be included in by quaternized, replace or oxidation modification before corresponding to following formula:
Modified polyamine formula V is arranged
(n+1)W
mY
nThe polyamine main chain of Z or by quaternized, replace or oxidation modification before corresponding to following formula:
Modified polyamine formula V is arranged
(n-k+1)W
mY
nY '
kThe polyamine main chain of Z, wherein k is less than or equal to n, and described polyamine main chain had before modification greater than 200 daltonian molecular weight, wherein
I) the V unit is the terminal units of following formula:
Ii) the W unit is the backbone units of following formula:
Or
Or
Iii) the Y unit is the branching unit of following formula:
Iv) the Z unit is the terminal units of following formula:
Wherein main chain connection R unit is selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-, and composition thereof; R wherein
1Be C
2-C
6Alkylidene group and composition thereof; R
2For hydrogen ,-(R
1O)
xB and composition thereof; R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl, and composition thereof; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, and composition thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and composition thereof; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3, and composition thereof; Condition is when any E unit of nitrogen is hydrogen, and described nitrogen neither the N-oxide compound; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and composition thereof; M is sufficient hydrogen or the water-soluble cationic that satisfies charge balance; X is a water soluble anion; M has 4 to 400 value; N has 0 to 200 value; P has 1 to 6 value, and q has 0 to 6 value; R has 0 or 1 value; W has 0 or 1 value, and x has 1 to 100 value; Y has 0 to 100 value; Z has 0 or 1 value.
2. the method for claim 1 also is included in the described slip of formation and makes described acid-sensitive polymer dispersed form the step of pre-composition in carrier before.
3. the method for claim 1 also comprises the step of described slip spraying drying being made cleanser compositions.
4. the method for claim 1 also is included in and forms described slip adds water glass before in described and in the activated detergent step.
5. the process of claim 1 wherein described basic material be selected from carbonate, phosphoric acid salt, silicate, layered silicate, oxyhydroxide, and composition thereof.
6. the method for claim 2, wherein the weight ratio of carrier and acid-sensitive polymkeric substance is at least 1: 1.
7. the method for claim 2, wherein said carrier comprises water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/025160 WO2000031226A1 (en) | 1998-11-25 | 1998-11-25 | Process for forming a cleaning composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1322233A CN1322233A (en) | 2001-11-14 |
| CN1162531C true CN1162531C (en) | 2004-08-18 |
Family
ID=22268368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988143283A Expired - Fee Related CN1162531C (en) | 1998-11-25 | 1998-11-25 | Process for forming cleaning composition |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1133544B1 (en) |
| JP (1) | JP2002530516A (en) |
| CN (1) | CN1162531C (en) |
| AR (1) | AR021384A1 (en) |
| AT (1) | ATE243251T1 (en) |
| AU (1) | AU1702699A (en) |
| BR (1) | BR9816085A (en) |
| CA (1) | CA2348891A1 (en) |
| DE (1) | DE69815723T2 (en) |
| ES (1) | ES2196635T3 (en) |
| WO (1) | WO2000031226A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6511956B1 (en) * | 1998-11-25 | 2003-01-28 | The Procter & Gamble Company | Process for forming a cleaning composition |
| CN116656706B (en) * | 2023-04-18 | 2024-08-20 | 河南中医药大学第一附属医院 | Recombinant plasmid of acid-sensitive fusion protein and construction and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
| EP0618289B1 (en) * | 1993-03-30 | 1998-08-19 | The Procter & Gamble Company | High active granular detergents comprising chelants and polymers, and processes for their preparation |
| EP0688862A1 (en) * | 1994-06-24 | 1995-12-27 | The Procter & Gamble Company | Structured detergent pastes and a method for manufacturing detergent particles from such pastes |
| CN1221448A (en) * | 1996-04-17 | 1999-06-30 | 普罗格特-甘布尔公司 | High density detergent-making process using high active surfactant paste having improved stability |
| DE69707480T2 (en) * | 1996-08-26 | 2002-08-14 | THE PROCTER & GAMBLE COMPANY, CINCINNATI | SPRAY DRYING METHOD FOR PRODUCING DETERGENT COMPOSITIONS WITH PRE-MIXING OF A MODIFIED POLYAMINE |
| JP2000501453A (en) * | 1996-08-26 | 2000-02-08 | ザ、プロクター、エンド、ギャンブル、カンパニー | Agglomeration method for producing detergent compositions including premixing of modified polyamine polymer |
-
1998
- 1998-11-25 CA CA002348891A patent/CA2348891A1/en not_active Abandoned
- 1998-11-25 ES ES98961786T patent/ES2196635T3/en not_active Expired - Lifetime
- 1998-11-25 AT AT98961786T patent/ATE243251T1/en not_active IP Right Cessation
- 1998-11-25 DE DE69815723T patent/DE69815723T2/en not_active Expired - Lifetime
- 1998-11-25 AU AU17026/99A patent/AU1702699A/en not_active Abandoned
- 1998-11-25 JP JP2000584039A patent/JP2002530516A/en active Pending
- 1998-11-25 CN CNB988143283A patent/CN1162531C/en not_active Expired - Fee Related
- 1998-11-25 WO PCT/US1998/025160 patent/WO2000031226A1/en active IP Right Grant
- 1998-11-25 BR BR9816085-0A patent/BR9816085A/en not_active IP Right Cessation
- 1998-11-25 EP EP98961786A patent/EP1133544B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2000031226A1 (en) | 2000-06-02 |
| EP1133544A1 (en) | 2001-09-19 |
| DE69815723T2 (en) | 2004-04-29 |
| EP1133544B1 (en) | 2003-06-18 |
| ATE243251T1 (en) | 2003-07-15 |
| AU1702699A (en) | 2000-06-13 |
| CA2348891A1 (en) | 2000-06-02 |
| JP2002530516A (en) | 2002-09-17 |
| AR021384A1 (en) | 2002-07-17 |
| ES2196635T3 (en) | 2003-12-16 |
| BR9816085A (en) | 2001-08-14 |
| CN1322233A (en) | 2001-11-14 |
| DE69815723D1 (en) | 2003-07-24 |
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