CN104364363A - Granulated foam control composition - Google Patents

Abstract

A granulated foam control composition comprises a foam control agent based on a polydiorganosiloxane fluid, an organic additive of melting point 45DEG C to 100DEG C comprising a polyol ester, a water-soluble particulate inorganic carrier, a polymer having a net cationic charge and a surfactant. The mean number of carbon atoms in the organo groups of the polydiorganosiloxane fluid is at least 1.3. The foam control agent includes a hydrophobic filler dispersed in the polydiorganosiloxane fluid, and optionally an organosilicone resin. The polyol ester is miscible with the polydiorganosiloxane fluid.

Description

Granulating Sudo controlling compositions

The present invention relates to for the silicone base Sudo controlling compositions for aqueous composition easy to foaming.Sudo controlling compositions of the present invention can add detergent composition particularly detergent powder to, to suppress excess foaming at detergent use in time washing.

In some countries, washing by hand clothes is a regular practice.The water that this process need is a large amount of, and water possibility is rare or be difficult to obtain.Therefore, develop and can be added on to reduce the suitable particles defoamer of the foam in rinse cycle in laundry detergent powder, will by reducing rinsing times thus reducing water loss and be of value to human consumer.But in order to not change the custom of human consumer, this granulating defoamer should greatly not reduce the foam produced in washing step process.When wash by hand wash time, or in incomplete automatization thus user sees that when washing in the washing machine of independent washing and rinse step, human consumer is desirably in washing step process and sees foam.Defoamer should than substantially more effectively reducing foam in washing step process in rinse step process.

Foam control granules according to the present invention comprises:

(A) Foam Control, it comprises

I () comprises the polydiorganosiloxane fluid of the unit of following formula

Wherein each radicals R can be identical or different, and be selected from the alkyl group with 1-36 carbon atom or have aromatic yl group or the aromatic alkyl group of the most nearly 36 carbon atoms, the average number of the carbon atom in described radicals R is at least 1.3;

(ii) dewatering filling in described polydiorganosiloxane fluid is dispersed in; With

(iii) optional silicone resin;

(B) fusing point 45 DEG C-100 DEG C comprises the organic additive of polyol ester, described polyol ester is had the polyvalent alcohol of the carboxylate completely or partially esterification of 7-36 carbon atom separately, and miscible with described polydiorganosiloxane fluid (A) (i);

(C) water-soluble granular inorganic carrier;

(D) there is the polymkeric substance of clean cationic charge; With

(E) tensio-active agent.

The present invention also comprises the granulating Sudo controlling compositions comprising the particle limited above reduces the foam in rinse step process purposes when it is incorporated in laundry detergent powder.

A kind of method manufacturing granulating Sudo controlling compositions according to the present invention comprises:

-mixing

(A) Foam Control, it comprises

I () comprises the polydiorganosiloxane fluid of the unit of following formula

Wherein each radicals R can be identical or different, and be selected from the alkyl group with 1-36 carbon atom or have aromatic yl group or the aromatic alkyl group of the most nearly 36 carbon atoms, the average number of the carbon atom in described radicals R is at least 1.3;

(ii) dewatering filling in described polydiorganosiloxane fluid is dispersed in; With

(iii) optional silicone resin; With

(B) fusing point 45 DEG C-100 DEG C comprises the organic additive of polyol ester, described polyol ester is had the polyvalent alcohol of the carboxylate completely or partially esterification of 7-36 carbon atom separately, and miscible with described polydiorganosiloxane fluid (A) (i); And

-mixture of (A) and (B) is deposited on water-soluble granular inorganic carrier, the mixture of (A) and (B) is gone forward as non-aqueous liquid form being deposited on water-soluble granular inorganic carrier; And

-with the mixture of (A) and (B) simultaneously or thereafter, will there is the polymkeric substance (D) of clean cationic charge and (E) surfactant deposition on water-soluble granular inorganic carrier.

Polydiorganosiloxane fluid (i) preferably have be no more than 5 % by mole branching units as RSiO _3/2unit or crosslink sites, be most preferably less than the branching units of 2 % by mole.The average number of the carbon atom in described radicals R preferably at least 1.3, more preferably at least 2.0, most preferably at least 2.5, if described radicals R does not comprise aryl or aromatic alkyl group.Polydiorganosiloxane fluid does not contain non-silicone polymer chain as polyether chain.

A preferred example of polydiorganosiloxane fluid is such polysiloxane, and it comprises two diorganosiloxane units of the following formula of at least 10%

Reach most two diorganosiloxane units of the following formula of 90%

, wherein X represents the divalent aliphatic organic group by carbon atom and silicon bonding; Ph represents aromatic group; Y represents the alkyl group with 1-4 carbon atom; And Y' represents the aliphatic hydrocarbon group with 1-24 carbon atom, described in EP1075864.Two diorganosiloxane units containing-X-Ph group preferably account for the 5%-60% of two diorganosiloxane units in described fluid.Radicals X preferably has the divalent alkylene groups of 2-10 carbon atom, most preferably 2-4 carbon atom, but alternatively can contain ehter bond between two alkylidene groups or between alkylidene group and-Ph, or can contain ester bond.Ph most preferably is phenyl group, but can such as be replaced by one or more methyl, methoxyl group, hydroxyl or cl radical, or two substituting groups on Ph group can form divalent alkylene groups together, or can form aromatic ring together, thus cause becoming such as naphthylene group with Ph halogen in combination.Particularly preferred X-Ph group is 2-phenyl propyl-CH ₂-CH (CH ₃)-C ₆h ₅.Group Y is preferably methyl, but can be ethyl, propyl group or butyl.Group Y' preferably has 1-18, most preferably 2-16 carbon atom, such as ethyl, methyl, propyl group, isobutyl-or hexyl.The mixing of alkyl group Y' can be used, such as ethyl and methyl, or the mixing of dodecyl and tetradecyl.Other groups can be there are, such as directly and the halogenated alkyl group (as chloropropyl) of Si bonding, acyloxyallcyl or alkoxy-alkyl group or aromatic group (as phenyl).

Polysiloxane fluid (A) (i) containing-X-Ph group can be substantial linear siloxane polymer, or certain side chain can be had, such as, because there are some trifunctional siloxane units, there is side chain in siloxane chain, or there is side chain, as described in EP-A-1075684 because connecting multivalence (such as divalence or the trivalent) organic moiety of polymer chain or silicon-organic moiety.

The example of the alternative of preferred polydiorganosiloxane fluid is such polysiloxane, and it comprises two diorganosiloxane units of the following formula of 50%-100%

With two diorganosiloxane units optionally reaching most the following formula of 50%

, wherein Y represents the alkyl group with 1-4 carbon atom, and Z represents the alkyl group with 6-18 carbon atom.Group Y in this polydiorganosiloxane is preferably methyl or ethyl.Alkyl group Z preferably can have 6-12 or 14 carbon atoms, such as octyl group, hexyl, heptyl, decyl or dodecyl, or the mixing of dodecyl and tetradecyl.

Preferably, the number (DP or the polymerization degree) of the siloxane unit in the mean molecule of the polysiloxane fluid of above arbitrary type is at least 5, more preferably 10-5000.Particularly preferably be the polysiloxane that DP is 20-1000, more preferably 20-200.The end group of polysiloxane can be any one in siloxanes in conventional those groups existed, such as trimethylsilyl terminal group.

Containing-X-Ph group polydiorganosiloxane fluid or containing-Z group polydiorganosiloxane fluid preferably as described Sudo controlling compositions polysiloxane fluid content at least 80 % by weight exist, most preferably as described polysiloxane fluid 100% or more than 95% existence.

Alternatively, polydiorganosiloxane fluid (i) can be that wherein organic group is all the polydiorganosiloxane of the alkyl group with 2-4 carbon atom substantially, such as polydiethylsiloxane.But this kind of polydiorganosiloxane fluid is also not preferred, because the foaming so effectively controlling from laundry detergent powder not as those Foam Controls described in EP-A-1075684 based on their Foam Control.

Described Sudo controlling compositions contains the dewatering filling (ii) be dispersed in described polydiorganosiloxane fluid.Dewatering filling for Foam Control is well-known, and be the granulated material for solid at 100 DEG C, as silicon-dioxide, (its surface-area is pressed BET method of masurement and measured preferably at least 50m ²/ g), the reaction product of the salt of titanium dioxide, silica powder, aluminum oxide, aluminosilicate, zinc oxide, magnesium oxide, aliphatic carboxylic acid, isocyanic ester and amine (such as hexahydroaniline) or alkylamide be as ethylenebisstearamide or methylene bis stearamide.The mixture of both or the more persons in these fillers can be used.

Some person's characters being had and non-hydrophobic in above-mentioned filler, if but make it become hydrophobic, can use.This can original position carry out (that is, when being scattered in polysiloxane fluid), or by being undertaken mixing with polysiloxane fluid after filler pre-treatment.Preferred filler is become hydrophobic silicon-dioxide.Preferred earth silicon material is that those pass through to add the earth silicon material of hot preparation (such as pyrogenic silica) or precipitation.Silica filler such as can have 0.5 μm-50 μm, the mean particle size of preferably 2 μm-30 μm, most preferably 5 μm-25 μm.It is by becoming hydrophobic by fatty acid treatment, but preferably by use methyl substituted organosilicon material and become hydrophobic, described methyl substituted organosilicon material is as dimethylsiloxane polymer (it is with the alkoxy base end-blocking of silanol or silicon bonding), hexamethyldisilazane, hexamethyldisiloxane or containing (CH ₃) ₃siO _1/2the silicone resin of group and silanol.Hydrophobization normally carries out at the temperature of at least 100 DEG C.The mixture of filler can be used, such as, the silica filler (silica filler as sold with trade mark " Sipernat D10 ") of very hydrophobic can use together with the silicon-dioxide of part hydrophobic (silicon-dioxide as sold with trade mark " Aerosil R972 ").

Dewatering filling (A) (ii) amount in Sudo controlling compositions of the present invention, in polysiloxane fluid (A) (i), be preferably 0.5-50 % by weight, more preferably 1 % by weight to reaching 10 % by weight or 15 % by weight, most preferably 2-8 % by weight most.

Described Sudo controlling compositions is preferably containing silicone resin (A) (iii) that be combined with described polydiorganosiloxane fluid.This silicone resin can improve the foam control efficiency of described polysiloxane fluid.This is for the polysiloxane fluid containing-X-Ph group especially definite (as described in EP-A-1075684), also definite for the polysiloxane fluid containing-Z group.In this polysiloxane fluid, the surface properties of described fluid modified by described resin.

Silicone resin (A) (iii) normally nonlinear siloxane resin, preferably by formula R' _asiO _4-a/2siloxane unit composition, wherein R' represents hydroxyl, hydrocarbon or hydrocarbonoxy radical, and wherein the mean value of a is 0.5-2.4.It is preferably by formula R " unit price trialkyl siloxy-(M) group and four senses (Q) the group SiO4/2 of 3SiO1/2 form, wherein R " represents monovalent hydrocarbon group.M group than preferably (is equivalent to formula R' with the number of Q group in the scope of 0.4:1-2.5:1 _asiO _4-a/2in a value be 0.86-2.15), more preferably 0.4:1-1.1:1, most preferably 0.5:1-0.8:1 (being equivalent to a=1.0 to a=1.33).

Silicone resin (A) (iii) is preferably at room temperature solid.Such as can carry out by heating in the presence of a base the molecular weight that condensation improves resin.Alkali can be such as aqueous solution or the alcoholic solution of potassium hydroxide or sodium hydroxide, such as, solution in methyl alcohol or propyl alcohol.Alternatively, can use and comprise M group, trivalent R " SiO _3/2(T) resin of unit and Q unit, or in silicone resin the most nearly the unit of 20% can be divalent unit R " 2SiO _2/2.Radicals R " preferably has the alkyl group of 1-6 carbon atom, such as methyl or ethyl, or can be phenyl.Particularly preferably be, existing R " in group at least 80%, be most preferably all methyl group substantially.Resin can be the resin of trimethylammonium end-blocking.

In polysiloxane fluid (A) (i), silicone resin (A) (iii) amount in defoamer is preferably 1-50 % by weight, particularly 2-30 % by weight, most preferably 4-15 % by weight.Silicone resin can be solvable or soluble in polysiloxane fluid.If resin is soluble in polysiloxane fluid, then the mean particle size of resin can be such as 0.5 μm-400 μm, preferably 2 μm-50 μm.

Fusing point is that the organic additive (B) of 45 DEG C-100 DEG C is miscible with polydiorganosiloxane fluid (A) (i).So-called " miscible " refers to that not show with each material of its ratio mixing existed in Sudo controlling compositions in liquid phase (that is, if necessary, fusing) is separated.This clarification by the liquid mixture when there is not any filler or resin and judging.If each liquid is miscible, then mixture is clarified and is kept a phase.If each liquid immiscible, then mixture is opaque and be divided into two-phase when standing.

Organic additive (B) can improve by the foam control efficiency of the composition of load.We find that the additive of fusing point at least 45 DEG C can improve foam control efficiency especially effectively in rinsing.Most preferably, the fusing point of the mixture of organic additive (B) and polydiorganosiloxane fluid (A) (i) is 45 DEG C-100 DEG C.

Organic additive (B) comprises polyol ester, and this polyol ester is by the polyvalent alcohol of the carboxylate partly or completely esterification separately with 7-36 carbon atom.Polyol ester is preferably the ester of glyceryl ester or higher polyol (as tetramethylolmethane or Sorbitol Powder).Polyol ester is preferably wherein carboxylate and has monocarboxylate or the polycarboxylate (such as dicarboxylic ester, tricarboxylic ester or tetracarboxylic ester) of 18-22 carbon atom separately.This polyol carboxylate often has the fusing point of at least 45 DEG C.Polyol ester can be the diester of dibasic alcohol (as ethylene glycol or propylene glycol), is preferably and has at least 14 carbon atoms, more preferably has diester, such as Unister E 275 formed by the carboxylic acid of 18-22 carbon atom.The example of preferred glyceryl ester comprises tristearin and has the glyceryl ester of saturated carboxylic acid of 20 or 22 carbon atoms, and the fusing point as sold with trade mark " Synchrowax HRC " is the material of 54 DEG C, and it it is believed that mainly C ₂₂the Witepsol W-S 55 of lipid acid, has some C ₂₀chain and C ₁₈chain.Suitable polyol ester is in addition the ester of tetramethylolmethane, as tetramethylolmethane four behenate and pentaerythritol tetrastearate.

Polyol ester can contain the lipid acid of different chain length, and this is usual in natural product.Organic additive (B) can be the mixture of polyol ester, the mixture of ester such as containing different carboxylate, as the mixture of glycerol tripalmitate and the mixture of tristearin or the mixture of tristearin and Synchrowax HRC or Unister E 275 and Synchrowax HRC.

Fusing point is that the organic additive (B) of 45-100 DEG C also can comprise the more much higher first alcohol ester of polarity.Preferred polarity polyol ester comprises the polyvalent alcohol of partial esterification, comprise glycerine and the monoesters of carboxylic acid or diester, such as Zerol, glyceryl monolaurate, Stearic diglyceride or the Glyceryl monobehenate with 8-30 carbon atom.The monoesters of glycerine and the mixture of diester can be used.The partial ester of other polyvalent alcohols also can use, such as propylene glycol monopalmitate, Arlacel-60 or ethylene glycol monostearate.

Organic additive (B) preferably by polydiorganosiloxane fluid (A) (i) in 10 % by weight-200 % by weight, most preferably by this polydiorganosiloxane fluid with 20 % by weight to the most nearly 100 % by weight or 120 % by weight being present in granulating Sudo controlling compositions.

The polymkeric substance (D) with clean cationic charge is cationic polymers or amphiphilic polymers.Amphoteric ion polymer of the present invention will have clean cationic charge, and the overall cationic charge namely on these polymkeric substance will exceed total anionic charge.The cationic charge density of polymkeric substance is in the scope of about 0.05 milliequivalent/g to about 12 milliequivalents/g.Electric density is by calculating the molecular weight of the net charge number of every repeating unit divided by repeating unit.Positive charge can be positioned on main polymer chain or polymer lateral chain.For the polymkeric substance with amine monomers, electric density depends on the pH of carrier.For these polymkeric substance, electric density is measured for 7 times at pH.Preferably, the electric density of polymkeric substance is in the scope of about 0.05 milliequivalent/g to about 7 milliequivalents/g.

The weight-average molecular weight Mw of cationic polymers usually at 80,000-4,000, between 000, preferably from 100,000 or 200,000 to reaching 4,000,000 most, even more preferably from 200,000 to reaching 1,500 most, 000 or 2,000,000, described molecular weight is measured relative to polyethylene oxide standard substance with refractive index (RI) detection by size exclusion chromatography.Moving phase used is that 20% methyl alcohol is in moisture MEA, 0.1M NaNO of 0.4M ₃, solution in 3% acetic acid, on Waters Linear Ultrahydrogel post, 2 series connection.Pillar and detector remain on 40 DEG C.Flow rate set is 0.5mL/min.

The most applicable polymkeric substance with clean cationic charge of the present invention has molecular weight inversely and electric density.Usually the most applicable under higher molecular weight compared with the polymkeric substance of low charge density, and the polymkeric substance of higher charge density is usually the most applicable under lower molecular weight.Charged polymkeric substance of the present invention has the cationic degree parameter being up to 50 dalton meq/g, and wherein cationic degree parameter-definition is that the product of molecular weight as defined above and electric density as defined above is divided by 1000 (Mw × CD/1000).

Compared to the suppression of foam in washing process, there is the suppression of polymkeric substance remarkable reinforced foam in rinsing of clean cationic charge.

The non-limitative example of dispersion enhancing agent has positively charged ion or zwitter-ion polysaccharide, protein and synthetic polymer.Cationic polysaccharide includes but not limited to cationic cellulose derivative, cationic guar derivative, chitosan and cationic starch.Cationic polysaccharide has from about 50,000 to about 4,000,000, preferably reaches most the molecular weight of 4,000,000 from about 100,000 or 200,000.

One group of preferred cationic polysaccharide shows in following formula I:

Wherein R ¹, R ², R ³respective is independently H, C _1-24alkyl (straight chain or side chain),

Wherein n is about 0 to about 10; Rx is H, C _1-24alkyl (straight chain or side chain) or or their mixing, wherein Z is water soluble anion, preferred chlorion, bromide anion, iodide ion, hydroxide radical, phosphate radical, sulfate radical, methylsulfate and acetate moiety; R ⁵be selected from H or C ₁-C ₆alkyl _ortheir mixing; R ⁷, R ⁸and R ⁹be selected from H or C ₁-C ₂₈the benzyl of alkyl, benzyl or replacement or their mixing.

R ⁴for H Huo person – (P) _m-H, or their mixing; Wherein P is the repeating unit of the addition polymer formed by cationic monomer.In one embodiment, cationic monomer is selected from methacryloyl amido trimethyl ammonium chloride, has the dimethyldiallylammonium of following formula:

It causes polymkeric substance or the multipolymer of the unit with following formula:

Wherein Z ' is water soluble anion, preferred chlorion, bromide anion, iodide ion, hydroxide radical, phosphate radical, sulfate radical, methylsulfate and acetate moiety or their mixing, and m is about 1 to about 100.Alkyl on the sugared ring of polymkeric substance replaces, and, is about in the scope of 0.01%-5% in Mei Tang unit in this polysaccharide on average, is more preferably about in the scope of 0.05%-2% at every glucose unit.

Preferred cationic polysaccharide comprises cationic hydroxy alkylcellulose.The example of cationic hydroxy alkylcellulose comprises the cationic hydroxy alkylcellulose that those have INCI title polyquaternium 10, as the cationic hydroxy alkylcellulose that those are sold with trade(brand)name Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymkeric substance; With trade(brand)name Softcat SK ^tMthe polyquaternium 67 sold, they are all sold by Gao company of liking to be beautiful (Amerchol Corporation, New Jersey Ai Ji water city (Edgewater NJ)); And with the polyquaternium 4 that trade(brand)name Celquat H200 and Celquat L-200 sells, can available from National Starch chemical company (National Starch and Chemical, New Jersey Ai Ji water city).Other preferred polysaccharide comprise with glycidyl C ₁₂-C ₂₂alkyl dimethyl ammonium chloride carries out quaternised Natvosol or hydroxypropylcellulose.The example of this polysaccharide comprises the polymkeric substance having INCI title polyquaternium 24, sell with trade(brand)name Quaternium LM 200, with the PG-Natvosol lauryl dimethyl amine ammonium chloride that trade(brand)name Crodacel LM sells, with the PG-Natvosol cocoyl alkyl dimethyl ammonium chloride that trade(brand)name Crodacel QM sells, with the PG-Natvosol stearyldimethylammonium chloride sold with trade(brand)name Crodacel QS, and alkyl dimethyl ammonium hydroxypropyl oxygen base ethyl cellulose.

In one embodiment of the invention, cationic polymers comprises cationic starch.Cationic starch is described " Modified Starches; Properties and Uses " (" modified starch, character and purposes ") (CRC press publishes (1986)) by D.B.Solarek, and at United States Patent (USP) the 7th, 135, No. 451 the 2nd hurdles the 33rd walk in the 4th hurdle the 67th row description.The present invention's cationic starch used can such as comprise account for cationic starch about 0 % by weight to about 70 % by weight amylose starch.Cationic starch such as can comprise cationic maize starch, its comprise account for cationic starch about 25 % by weight to about 30 % by weight amylose starch.In above embodiment, remaining polymkeric substance comprises amylopectin.

Preferred polysaccharide comprises cationic galactomannan, such as cation guar gum or positively charged ion Viscogum BE in addition.An example of cation guar gum is the quaternary ammonium derivative of hydroxypropylguar gum, sell (available from Rhodia (Rhodia in New Jersey Crane Bai Li city (Cranburry) with trade(brand)name Jaguar C13 or Jaguar Excel, Inc)), or sell (Aqualon, Wilmington City, Delaware, USA State (Wilmington)) with N-Hance.

About the detailed description of the cationic polymers of synthesis can be published in Journal of Macromolecular Science-Chemistry (" macromolecular science magazine: chemistry ") at M.Fred Hoover, A4 (6), 1327-1417 page, finds in the article in October, 1970.The whole disclosure of the article of Hoover is incorporated herein by reference.The example of suitable cationic polymers has those in paper manufacture, be used as the cationic polymers of retention aid.Description is had in " Pulp and Paper, Chemistry and Chemical Technology Volume III " (III rolls up for paper pulp and paper, chemistry and Chemical Engineering Technology) that they are edited at James Casey (1981).The molecular weight of these polymkeric substance at 2,000-5, in the scope of 000,000.When reading the present invention in conjunction with the article of Hoover and the books of Casey, the cationic polymers of synthesis of the present invention will be understood better.

Synthetic cationic polymers used in the present invention includes but not limited to the synthesis addition polymer of following formula (II):

Wherein R ¹, R ²hereafter defining with Z.Preferably, this linear polymer unit is formed by linear polymerization monomer.Linear polymerization monomer is defined as the monomer causing producing straight chain or branched chain polymer chain under the polymerizing condition of standard in this article, or alternatively, makes the monomer that polymeric linear is expanded.Linear polymerization monomer of the present invention has following formula:

But those skilled in the art recognize that, many useful linear monomers unit indirectly introduce, particularly vinylamine units, vinyl alcohol units, but not introduced by linear polymerization monomer approach.Such as, vinyl acetate monomer is just hydrolyzed formation vinyl alcohol units once be incorporated in main chain.For purposes of the present invention, linear polymer unit can directly be introduced, and is namely introduced by linear polymerization monomer, or indirectly introduces, namely introduced by precursor, as when vinyl alcohol cited hereinabove.

In above formula (II), each R ¹be hydrogen, C independently ₁-C ₁₂alkyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl ,-OR _a, or-C (O) OR _awherein R _abe selected from hydrogen and C ₁-C ₂₄alkyl and their mixing; Each R ²be hydrogen, hydroxyl, halogen, C independently ₁-C ₁₂alkyl ,-OR _a, replace or unsubstituted phenyl, replacement or unsubstituted benzyl, carbocylic radical, heterocyclic radical and their mixing; Each Z is hydrogen, halogen independently; The C of straight or branched ₁-C ₃₀alkyl, nitrilo ,-N (R ³) ₂;-C (O) N (R ³) ₂;-NHCHO (methane amide);-OR ³;-O (CH ₂) _nn (R ³) ₂;-O (CH ₂) _nn ⁺(R ³) ₃x ^–;

-C(O)OR ⁴；-C(O)O(CH ₂) _nN(R ³) ₂；-C(O)O(CH ₂) _nN ⁺(R ³) ₃X ^-；

-CO(CH ₂) _nN(R ³) ₂；-OCO(CH ₂) _nN ⁺(R ³) ₃X ^-；-C(O)NH-(CH ₂) _nN(R ³) ₂；

-C (O) NH (CH ₂) _nn ⁺(R ³) ₃x-;-(CH ₂) _nn (R ³) ₂; Or-(CH ₂) _nn ⁺(R ³) ₃x ^-;

Wherein each R ₃be hydrogen, C independently ₁-C ₂₄alkyl, C ₂-C ₈hydroxyalkyl, phenyl; The benzyl replaced and their mixing; Each R ₄be hydrogen or C independently ₁-C ₂₄alkyl and ; X is water soluble anion; N is 1-6; R ₅be hydrogen or C independently ₁-C ₆alkyl, or their mixing.The Z aromatics nitrogen heterocyclic ring that also the non-aromatic nitrogen heterocyclic of optional self-contained quaternary ammonium ion, the heterocycle comprising N-oxide portions, one or more nitrogen-atoms are quaternized; Wherein at least one nitrogen is the aromatics nitrogen heterocyclic ring of N-oxide compound; Or their mixing.Preferably, R ¹for hydrogen, C ₁-C ₄alkyl or-OR _aor-C (O) OR _a.Preferred R ²for hydrogen, C ₁-C ₄alkyl, and their mixing.The non-limitative example comprising the monomer be polymerized in addition mode of heterocycle Z unit comprises l-vinyl-2-pyrrolidone, 1-vinyl imidazole, quatemized vinylimidazol, 2-vinyl-1,3-dioxolane, 4-vinyl-1-tetrahydrobenzene 1,2-epoxide and 2-vinyl pyridine, 2-vinylpyridine N-oxide, 4-vinylpridine N-oxide compound.

The non-limitative example that can be made into the Z unit of original position formation cationic charge has-NHCHO unit and methane amide.Formulator can prepare the polymkeric substance or multipolymer that comprise methane amide unit, and some of them methane amide unit is hydrolyzed subsequently and forms vinyl-amine counterpart.

The synthetic cationic polymers used in the present invention and multipolymer comprise the Z unit with cationic charge, or comprise the Z unit causing generation meeting original position to form the unit of cationic charge.Such as, at least one Z group of per molecule can be selected from-O (CH ₂) _nn ⁺(R ³) ₃x ^–,-C (O) OR ⁴;-C (O) N-(R ³) ₂,-C (O) O (CH ₂) _nn (R ³) ₂,-C (O) O (CH ₂) _nn ⁺(R ³) ₃x ^-,-OCO (CH ₂) _nn (R ³) ₂,-OCO (CH ₂) _nn ⁺(R ³) ₃x ^-,-C (O) NH-(CH ₂) _nn (R ³) ₂,-C (O) NH (CH ₂) _nn ⁺(R ³) ₃x ^-,-(CH ₂) _nn (R ³) ₂,-(CH ₂) _nn ⁺(R ³) ₃x ^-, or comprise the quaternized aromatics nitrogen heterocyclic ring of the non-aromatic nitrogen heterocyclic of quaternary ammonium ion, the heterocycle comprising N-oxide portions, one or more nitrogen-atoms; Wherein at least one nitrogen is the aromatics nitrogen heterocyclic ring of N-oxide compound.When multipolymer of the present invention comprises more than a Z unit, form and will comprise positively charged ion unit at least about 1% in the monomer of described multipolymer.

The synthetic cationic polymers used in the present invention or multipolymer can comprise one or more cyclic polymer unit derived from ring type polymerization single polymerization monomer.Ring type polymerization single polymerization monomer is defined as in this article and causes producing cyclic polymer residue and the monomer playing the effect that polymeric linear is expanded under the polymerizing condition of standard.Preferred ring type polymerization single polymerization monomer of the present invention has following formula:

Wherein each R ⁴independently for containing olefin unit, its except with adjacent R ⁴unit is formed outside cyclic residue, and polymerization can also be made to expand; R ⁵for C ₁-C ₁₂the benzyl of straight chain or branched-chain alkyl, benzyl, replacement and their mixing; X is water soluble anion.R ⁴the non-limitative example of unit comprises the allylic moiety of allylic moiety and alkyl replacement.Preferably, the cyclic residue of gained is the six-ring comprising quaternary nitrogen atoms.R ⁵be preferably C ₁-C ₄alkyl, preferable methyl.An example of ring type polymerization single polymerization monomer is the dimethyldiallylammonium salt with following formula:

It causes polymkeric substance or the multipolymer of the unit with following formula:

Wherein represent that the index z of the polymerization degree is about 10 to about 50,000.

Non-limitative example for preferred synthetic cationic polymers of the present invention comprises and is selected from homopolymer and multipolymer prepared by following cationic monomer from one or more:

A) methacrylic acid N, N-dialkyl aminoalkyl ester, vinylformic acid N, N-dialkyl aminoalkyl ester, N, N-dialkylaminoalkyl acrylamide, N, N-dialkyl aminoalkyl Methacrylamide, quaternized methacrylic acid N, N-dialkyl aminoalkyl ester, quaternized vinylformic acid N, N-dialkyl aminoalkyl ester, quaternary ammonium N, N-dialkylaminoalkyl acrylamide, quaternary ammonium N, N-dialkyl aminoalkyl Methacrylamide

B) vinyl-amine and derivative, allylamine and derivative thereof,

C) vinyl imidazole, quatemized vinylimidazol and poly (dially dialkyl) ammonium chloride.Optionally, described multipolymer comprises and is selected from following second comonomer: acrylamide, N, N-dialkylacrylamides, Methacrylamide, N, N-dialkyl methacrylamides, vinylformic acid C ₁-C ₁₂alkyl ester, vinylformic acid C ₁-C ₁₂hydroxyalkyl acrylate, polyalkene glycol acrylates, methacrylic acid C ₁-C ₁₂alkyl ester, methacrylic acid C ₁-C ₁₂hydroxyalkyl acrylate, polyalkylene glycol methacrylic ester, vinyl-acetic ester, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and derivative, vinylformic acid, methacrylic acid, toxilic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido propyl group methylsulfonic acid (AMPS) and their salt.

Polymkeric substance optionally crosslinkable.Cross-linking monomer includes but not limited to glycol diacrylate, Vinylstyrene, divinyl.

Preferred cationic monomer comprises vinylformic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-dimethylamino ethyl ester (DMAM), [2-(ethacryloylamino) ethyl] trimethyl ammonium chloride (QDMAM), N, N-dimethylaminopropylacryl acid amides (DMAPA), N, N-dimethylaminopropyl Methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium chloride, methacryiamidopropyl trimethyl ammonium chloride (MAPTAC), quatemized vinylimidazol and diallyldimethylammonium chloride and their derivative.Preferred non-ionic co-monomers comprises: acrylamide, N, N-DMAA, C1-C4 alkyl acrylate, C1-C4 hydroxy alkyl acrylate, hydroxy ethyl methacrylate (HEA), hydroxypropyl acrylate, vinyl formamide, vinyl-acetic ester and vinyl alcohol, and their derivative.

Most preferred synthetic polymer is poly-(acrylamide-altogether-diallyldimethylammonium chloride), poly-(acrylamide-first acrylamidopropyl trimethyl ammonium chloride) (PAM-MAPTAC), poly-(acrylamide--N altogether, N-dimethyl amino ethyl methacrylate), poly-(acrylamide--N altogether, N-dimethyl amino ethyl methacrylate), poly-(hydroxyethylmethacry,ate-altogether-dimethyl amino ethyl methacrylate), poly-(acrylate-altogether-dimethyl amino ethyl methacrylate), poly-(acrylate-altogether-methacrylamidopropyltrimethyl trimethyl ammonium chloride), poly-(acrylamide-altogether-diallyldimethylammonium chloride-altogether-vinylformic acid) and poly-(acrylamide-methacrylamidopropyltrimethyl trimethyl ammonium chloride-altogether-vinylformic acid).

The other alternative synthetic cationic polymers being applicable to using in the present invention has polymine and derivative thereof.These can trade(brand)name Lupasol (the BASF stock company (BASF AG) of Ludwigshafen, Germany) commercially available available from.In one embodiment, described polythene derivative is the amide derivatives of polymine, sells with trade(brand)name Lupoasol SK.Also comprise oxyalkylated polymine; Alkyl polyethylene imine and Quaternary Polyethyleneimine.

The other alternative synthetic cationic polymers being applicable to using in the present invention has Polyamidoamine-epichlorohydrin (PAE) resin, and it is the condensation product that polyalkylene polyamine and poly carboxylic acid also react with Epicholorohydrin further.Prevailing PAE resin is the condensation product that diethylenetriamine and hexanodioic acid react with Epicholorohydrin subsequently.They can trade(brand)name Kymene available from Hercules group company (Hercules Inc.) (Wilmington City, Delaware, USA State) or with trade(brand)name Luresin available from BASF stock company (BASF AG).These polymkeric substance L.L.Chan edit ' Wet Strength resins and their applications ' (" wet-strength resins and application thereof "), there is description in TAPPI press in (1994).

Described tensio-active agent (E) can be selected from nonionogenic tenside, cats product, anion surfactant and zwitterionics, or their mixture.

Nonionogenic tenside can be such as oxyalkylated nonionogenic tenside, such as oxyethane and long-chain (fat) alcohol or (fat) acid such as C _14-15the condenses that the condenses of the condenses of alcohol, oxyethane and 7 moles of ethylene oxide polycondensations, oxyethane and amine or acid amides are formed, or the condensation product of oxyethane and propylene oxide.More suitably nonionogenic tenside comprises the ester of silicone polyoxyalkylene multipolymer, fatty acid alkyl alcohol amide, fatty amine oxide, sucrose, glycerine or sorbyl alcohol, and fluorochemical surfactant.

Suitable nonionogenic tenside comprises alkyl polyglucoside and/or alkyl alkoxylated alcohol.Preferred nonionic alkyl alkoxylated alcohol comprises C _8-18alkyl alkoxylated alcohol, preferred C _8-18alkyl ethoxylated alcohol, preferably, the average degree of alkoxylation of alkyl alkoxylated alcohol is 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10, preferably, alkyl alkoxylated alcohol is the C of the average degree of ethoxylation with 1 to 10, preferably 1 to 7, more preferably 1 to 5 and most preferably 3 to 7 _8-18alkyl ethoxylated alcohol.That alkyl alkoxylated alcohol can be straight chain or side chain, and can be replacement or unsubstituted.Suitable nonionogenic tenside can be selected from: C ₈-C ₁₈alkylethoxylate, such as derives from Shell's nonionogenic tenside; C ₆-C ₁₂alkyl phenolic alkoxy thing, wherein preferably, described alcoxylates unit is ethyleneoxy units, propyleneoxy units or its mixing; C ₁₂-C ₁₈alcohol and C ₆-C ₁₂the condenses of alkylphenol and ethylene oxide/propylene oxide block polymer, such as, derive from BASF's c ₁₄-C ₂₂mid-chain branched alcohol; C ₁₄-C ₂₂mid-chain branched alkyl alkoxylates, preferably has the average degree of alkoxylation of 1 to 30; Alkyl polysaccharide, preferred alkyl polysaccharide glycosides; Polyhydroxy fatty acid amide; Ether capped poly-(alkoxylate) alcohol tensio-active agent.The mixture of two or more nonionogenic tensides can be used.

Anion surfactant can comprise sulfate surfactant and sulfosalt surfactant.Preferred sulfosalt surfactant comprises alkylbenzene sulfonate, preferred C _10-13alkylbenzene sulfonate.Suitable alkylbenzene sulfonate (LAS) is available, carries out sulfonation to obtain preferably by the linear alkylbenzene (LAB) to commercially available acquisition; Suitable LAB comprises rudimentary 2-phenyl LAB, such as by Sasol with trade(brand)name there is provided those, or by Petresa with trade(brand)name there is provided those, another kind of suitable LAB comprises senior 2-phenyl LAB, such as by Sasol with trade(brand)name there is provided those.Suitable anion surfactant is the alkylbenzene sulfonate obtained by DETAL catalysis process, but other route of synthesis such as HF also can be suitable.Preferred sulfate surfactant comprises alkyl-sulphate, preferred C _8-18alkyl-sulphate, or be mainly C ₁₂alkyl-sulphate.Another kind of preferred sulfate surfactant is alkyl alkoxylated vitriol, the vitriol (AES) of preferred alkyl ethoxylation, preferred C _8-18alkyl alkoxylated vitriol, preferred C _{8- 18}the vitriol of alkyl ethoxylated, preferably have 0.5 to 20, the preferably alkyl alkoxylated vitriol of average degree of alkoxylation of 0.5 to 10, preferably, described alkyl alkoxylated vitriol has 0.5 to 10, preferably 0.5 to 7, more preferably 0.5 to 5 and most preferably 0.5 to 3 the C of average degree of ethoxylation _8-18the vitriol of alkyl ethoxylated.That described alkyl-sulphate, alkyl alkoxylated vitriol and alkylbenzene sulfonate can be straight chain or side chain, replacement or unsubstituted.

Suitable organic anion surfactant comprises alkylaryl sulphonate (such as Sodium dodecylbenzene sulfonate), long-chain (fat) alcohol sulfate, olefin sulphates and sulfonate, sulfonic acid direactive glyceride, sulphonate, the alcohol of the alcohol of sulfonic acid ethoxylation or sulfuric acid ethoxylation, sulfosuccinate, alkane sulfonate, the metal alkylide soap of higher fatty acid, phosphoric acid ester, alkyl isethionate, alkyl tauride and/or alkyl sarcosine salt.The mixture of two or more anion surfactants can be used.

Suitable cats product comprises alkyl pyridinium compounds, alkyl quaternary ammonium compound, Wan Ji quaternary phosphonium compound, alkyl ternary sulphonium compounds, and their mixture.Preferred cats product is the quaternary ammonium compound with following general formula:

(R ¹⁰)(R ¹¹)(R ¹²)(R ¹³)N ⁺X ^-

Wherein, R ¹⁰straight chain or side chain, replace or unsubstituted C _6-18alkyl or alkenyl part, R ¹¹and R ¹²independently selected from methyl or aminoethyl moiety, R ¹³for hydroxyl, methylol or hydroxyethyl moieties, X is for providing electroneutral negatively charged ion, and preferred negatively charged ion comprises: halogen, is preferably chlorion; Sulfate radical; And sulfonate radical.Preferred cationic detersive surfactants is single-C _6-18alkyl list hydroxyethyl dimethyl aliquat.Highly preferred cationic detersive surfactants is single-C _8-10alkyl list hydroxyethyl dimethyl aliquat, list-C _10-12alkyl list hydroxyethyl dimethyl aliquat and single-C ₁₀alkyl list hydroxyethyl dimethyl aliquat.

Cats product can be such as alkylamine salt, quaternary ammonium salt, sulfonium salt Huo phosphonium salt.The mixture of two or more cats products can be used.

Zwitter-ion (both sexes) tensio-active agent can be such as imidazolinium compounds, alkylaminoacid salts or trimethyl-glycine.The mixture of two or more zwitterionicss can be used.

Compared in washing process to the suppression of foam, tensio-active agent (E) enhances the effect that the polymkeric substance (D) with clean cationic charge suppresses the foam in rinsing, and also improves stability in storage.

The weight ratio of the polymkeric substance (D) and tensio-active agent (E) with clean cationic charge generally can be 1:10 to 100:1, and is preferably 1:9 to 9:1, more preferably 1:5 to 9:1.

Can easily by admixed together to the polymkeric substance (D) and tensio-active agent (E) with clean cationic charge before mixing with other components of Foam control granules, but they can separately add.

The example of water-soluble inorganic carrier (C) is phosphoric acid salt, such as powdered or granular tripoly phosphate sodium STPP; Vitriol, such as sodium sulfate and potassium sulfate; Carbonate, such as sodium carbonate, as anhydrous sodium carbonate or crystal carbonate, concentrated crystal soda, and sodium bicarbonate, salt of wormwood and saleratus; Silicate, such as water glass; Citrate trianion, such as Trisodium Citrate and Tripotassium Citrate; Acetate, such as sodium acetate; And muriate, such as sodium-chlor and Repone K.Preferred carrier (C) comprises sodium sulfate, sodium carbonate and sodium bicarbonate.The particle diameter of water-soluble inorganic carrier is preferably in the scope of 1 μm-40 μm, and more preferably 1 μm extremely most reaches 20 μm or 30 μm.

We find compared with water insoluble carrier, use water-soluble granular inorganic carrier obviously can improve the performance of granulating Sudo controlling compositions of the present invention.Specifically, the granulating Sudo controlling compositions comprising water-soluble granular carrier more effectively can reduce the foam in rinse stage.But, water-insoluble bead-type substrate can be used as a part for the carrier component of particle of the present invention.Suitable water insoluble carrier example comprises zeolite, such as Wessalith CS or X zeolite, other aluminosilicates or silicate, such as Magnesium Silicate q-agent and silicon-dioxide.Zeolite is preferred water-insoluble bead-type substrate.If use water-insoluble bead-type substrate in particle of the present invention, then it is preferably formed and is no more than 20% of total bead-type substrate by weight, more preferably no more than 10%.Water-soluble granular carrier and water-insoluble bead-type substrate can mix with drying particulate form easily before mixing with other components of Foam control granules.

Generally Foam Control (A), organic additive (B), cationic polymers (D) and tensio-active agent (E) can be added in carrier particle respectively, or carry out pre-mixing with arbitrary combination.Preferably the Foam Control (A) of the polysiloxane fluid (i) comprised containing dewatering filling (ii) and optional silicone resin (iii) is mixed with organic additive (B).By mixture preferably with non-aqueous deposited in liquid form on carrier particle.

With the mixture of (A) and (B) simultaneously or thereafter, cationic polymers (D) and tensio-active agent (E) can be deposited on carrier particle (C) separately or together.If cationic polymers (D) and tensio-active agent (E) are deposited on carrier particle with the mixture of (A) and (B) simultaneously, then can make cationic polymers (D) and tensio-active agent (E) and (A) and (B) pre-mixing, or by same nozzle or independent nozzle, the mixture of cationic polymers (D) and tensio-active agent (E) and (A) and (B) is deposited on carrier particle (C) simultaneously.Such as, first can prepare the mixture of (D) and (E), in (D) and (E), then add the mixture of (A) and (B).The mixture of cationic polymers (D) and tensio-active agent (E) generally deposits in liquid form, such as, is deposited by aqueous solution or dispersion.The drying of cationic polymer solution contributes to carrier particle to combine to form particle.

Preferably to make polydiorganosiloxane fluid (A) (i) content in Foam control granules be that the ratio of 1% to 25% of Foam control granules by weight comes mix-froth control agent (A), organic additive (B), cationic polymers (D), tensio-active agent (E) and carrier particle (C).Preferably, the polydiorganosiloxane fluid content of described particle is 1% to 15%, preferably 2% to 15%, preferably 5% to 15%, preferably 7% to 12%.

Preferably the mixture of (A) and (B) is deposited on carrier particle at organic additive (B) temperature that is liquid, such as, temperature within the scope of 45 DEG C-100 DEG C.Along with mixture cools on carrier particle, it is solidified into the structure contributing to the efficiency improving Sudo controlling compositions.The mixture of (A) and (B) of solidification also can play the effect making carrier particle combine to be formed particle.The Sudo controlling compositions of load is prepared preferably by agglomeration method, in agglomeration method, is sprayed on carrier particle, stirs particle simultaneously by the Sudo controlling compositions comprising Foam Control (A) and organic additive (B).Particle is preferably stirred in this high shear mixer continuously across high shear mixer.

Optionally, can before agglomeration process or period, that is, before the deposition of Foam Control (A), organic additive (B), cationic polymers (D) and tensio-active agent (E) or period easily carrier particle (C) is heated.Carrier particle can >=30 DEG C or >=40 DEG C, or >=50 DEG C, or the temperature range heating of >=70 DEG C.

The suitable mixer of one type is the continuous high shear mixer of vertical type, and Sudo controlling compositions is sprayed on particle wherein.An example of this mixing machine is the Flexomix mixing machine supplied by Hosokawa Schugi.If the mixture of (D) and (E) and the mixture of (A) and (B) are deposited on water-soluble granular inorganic carrier through fog nozzle, then can before being about to spray, such as, make the mixture of the mixture of (D) and (E) and (A) and (B) admixed together in the top of described nozzle.

Spendable suitable mixer in addition comprises horizontal high shear mixer, in mixing section, wherein form the circular layer of powder-liquid mixture, and the residence time is that a few second is extremely up to about 2 minutes.The example of the machine of this family has leaf formula mixing machine (pin mixer) (the TAG series of such as being supplied by LB, from the RM type machine of Rubberg-Mischtechnik or the leaf formula mixing machine supplied by Lodige) and paddle stirrer (CB such as supplied by Lodige is serial, from the Corimix (trade mark) of Drais-Manheim, Conax (trade mark) machine from Ruberg Mischtechnik).

Other possible mixing machines that can use in the method for the invention have Glatt granulator, ploughshare mixing machine (such as being sold by Lodige GmbH), the bitubular is to rotary propeller type mixing machine (being called Forberg (trade mark) type mixing machine), the intensive mixer of high shear mixing arm is comprised (as " Typ R " machine that Eirich sells in turning circle cylindrical container, from Zig-Zag (trade mark) mixing machine and HEC (trade mark) machine sold by Niro of Patterson-Kelley.

Another kind of possible prilling process is fluidized-bed.The example of fluidized bed prilling machine has Glatt fluidized-bed and Aeromatic/Niro fluidizer.In fluidized-bed, by liquid dispersion (solution, suspension or emulsion) is atomised on suspended particles bed and agglomeration occurs, to prepare particle.

No matter use which kind of prilling process, all by the liquid component of Sudo controlling compositions, carrier particle is combined, to form particle.Each Foam control granules is comprised and is multiplely coated with liquid composition and the water-soluble inorganic carrier particle (C) combined by liquid composition, and described liquid composition comprises Foam Control (A), organic additive (B), the polymkeric substance (D) with clean cationic charge and tensio-active agent (E).Granulating Sudo controlling compositions can easily mix in detergent powder.Be at least 0.1mm according to the usual median size of particle that the present invention produces, preferably greater than 0.25mm or 0.5mm, be up to the mean diameter of 1.2mm or 1.5mm or even 2mm.We find, the particle (especially 0.5mm-1mm) according to this granularity of the present invention has good flowing property and resistance to compactibility.

Granulating Sudo controlling compositions of the present invention can containing other composition, if density adjuster, color care agents are if maleic acid ester or fumarate (two (2-methoxyl group-1-ethyl) ester of such as toxilic acid or diallyl maleate), acetylene alcohol (such as methylbutynol or cyclooctadiene), thickening material are if the pyrogenic silica of carboxymethyl cellulose, polyvinyl alcohol or hydrophilic or part hydrophobic or tinting material are as pigment or dyestuff.

Granulating Sudo controlling compositions of the present invention adds detergent powder to 0.1-10 % by weight, preferably 0.2-0.5 or 1.0% usually.Detergent composition can be such as that those have the detergent composition of the anion surfactant (such as Sodium dodecylbenzene sulfonate) of high-content.When middle for laundry detergent (such as laundry detergent powder); find that granulating Sudo controlling compositions of the present invention has a certain impact (such as to foam tool in washing process; foam lower than 30% reduces); in first time rinsing, foam tool is had a great impact (such as, reducing higher than the foam of 50%) simultaneously.Find that this is real when washing by hand clothes, and be also real when washing clothes with semiautomatic machine.

The present invention is set forth by following instance, and wherein number and per-cent are by weight, and wherein uses following testing method.

washing foam exponential sum rinsing foam index

Washing foam index is used for the lather volume that containing the independent laundry detergent of of the present invention granulating Sudo controlling compositions do not produce of the lather volume produced by the laundry detergent of the present invention comprising granulating Sudo controlling compositions in the washing stage with thing in contrast to compare.In this article, this lather volume is measured by the foam height after standard laundry method described below.

After the independent laundry detergent of the lather volume remaining after being used for rinsing being comprised the laundry detergent of the present invention of granulating Sudo controlling compositions of rinsing foam index and rinsing thing in contrast, the lather volume of remnants compares.In this article, amassed by the foam surface in the Washing basin after standard rinse method described below and measure this lather volume.

Laundry detergent of the present invention for performing described experiment comprises by laundry detergent weighing scale, the granulating Sudo controlling compositions of the present invention of 0.5% and contrast granulating Sudo controlling compositions, the linear alkylbenzene sulfonate of 11%, the alkyl dimethyl hydroxyethylammonium chloride of 1%, the moles average ethoxylation degree of 3.5% is the alcohol of the C14-15 alkyl ethoxylated of 9, the sodium aluminium silicate (zeolite) of 20%, the sodium carbonate of 15%, the sodium sulfate of 28%, the water glass of 2%, the carboxymethyl cellulose of 1.5%, the polyacrylic acid of 4%, the SPC-D of 2%, the tetra-acetylated ethylene diamine (TAED) of 0.5%, and comprise enzyme etc., wherein the total amount of all components is added up and equal 100%.

Standard laundry method:

1) in basin, load 2L deionized water (4gpg), dissolve laundry detergent, to reach the concentration of 3500ppm in water, carry out whirlpool and stir 2 minutes, until laundry detergent dissolves completely and forms laundry liquid.

2) fabric is put into laundry liquid, and soak 5 minutes.

3) for every part fabric, rub 5 times, all put back in laundry liquid at every turn between rubbing and soak.

4) the stubborn fabric rubbed gently, does not disturb generation foam.

5) measure the total height of foam and laundry liquid, carry out comprising a central point of basin and five measurements of four marginal points, average;

6) height of laundry liquid in basin is measured after defoaming from basin;

7) by by step 5) observed value deduct step 6) observed value obtain foam height.

Standard rinse method:

1) fabric pieces through washing and through being threaded through is put into the new basin comprising 2L fresh deionized water (4gpg), laundry liquid carrying amount is controlled to be 200 ± 5g (weight of the gross weight-dry fabric after carrying amount=washing).Softly washed by rubbing with the hands by 3 times and rinsing is carried out to each fabric pieces.

2) from water, fabric pieces is being removed after 5 seconds to 10 seconds, the photo of the foam deck on shooting rinse water surface.

For the sake of simplicity, setting is provided in following table 1 for washing the condition with rinse method.

table 1

example

example 1 and comparative example 1

Granulating Sudo controlling compositions according to the present invention is prepared as follows:

By by weight (6%) 6 percent the partially hydrophobic silicon-dioxide deriving from Evonik with trade(brand)name R972 through precipitated silica and 1% deriving from the process of Evonik with trade(brand)name Sipernat D10 be scattered in the polydiorganosiloxane fluid of 86.3%, described polydiorganosiloxane fluid has the polymerization degree of 65, and comprises the methyl dodecyl siloxane group of 80 % by mole and methyl 2-hydrocinnamyl (spreading out from the alpha-methyl styrene) siloxane groups of 20 % by mole.Add the following solution of 6.7 % by weight: organosiloxane resins (M/Q ratio is 0.65/1) 60 % by weight solution in octyl stearate with trimethyl siloxane units and SiO2 unit.Gained mixture carries out homogeneous through high shear mixer, to form Foam Control FC1.

First time passes through: the tristearin provided by Sa Suoer company (Sasol) of the Foam Control FC1 and 38.00 of 62.00 weight parts part is carried out mechanically mixing.The tristearin of FC1 and fusing is mixed at 90 DEG C.Tristearin and polydiorganosiloxane fluid miscible, the fusing point of mixture is 74 DEG C.

By the tristearin of 18.25 parts and the mixture of FC1 in Schugi Flexo mixing machine, be sprayed in the sodium sulfate powder of 77.55 parts with the water of 4.20 parts by two nozzles be separated, to generate granular granulated material simultaneously.The water comprised in this granulating Sudo controlling compositions is removed in fluidized-bed.

Second time is passed through: by 47.15 parts of polyacrylamide methacryiamidopropyl trimethyl ammonium chloride (PAM MAPTAC) cationic polymerss, 5.70 portions of C14-15AE7 nonionogenic tensides and 47.15 parts of water mechanically mixing.

By putting back in Schugi Flexo mixing machine by the particulate state granulated material obtained with the amount of 97.32 parts from first time, wherein 2.68 parts of PAM MAPTAC/ nonionogenic tenside aqueous solutions are sprayed thereon.The water comprised in this granulating Sudo controlling compositions is removed in fluidized-bed.The granulating Sudo controlling compositions of gained is labeled as example 1.

Test comprise granulating Sudo controlling compositions according to of the present invention laundry detergent and the scope of the invention outside the rinsing foam of laundry detergent remove.

comparative example 1: the granulating Sudo controlling compositions outside the scope of the invention uses method mentioned above to prepare, but, in second time is passed through, do not add C14-15AE7 nonionogenic tenside.The substitute is, by 50 parts of PAM MAPTAC cationic polymerss and 50 parts of water mechanically mixing (pre-composition 4).By putting back in Schugi Flexo mixing machine by the particulate state granulated material obtained with the amount of 97.32 parts from first time, wherein add 2.68 parts of PAM MAPTAC aqueous solutions.The granulating Sudo controlling compositions of gained is labeled as comparative example 1.The general view of particulate composition can be seen in table 2.

table 2

% by weight	Foam Control	Organic additive	Granular inorganic carrier	Cationic polymers	Nonionogenic tenside
						Example 1	11.78	7.22	80.76	0.08	0.16
Comparative example 1	11.80	7.23	80.88	0.09	0

Example 1 and comparative example 1 (0.5 % by weight) are added into existing comprising in " can be purchased off the shelf " granular laundry detergent composition of anionic detersive surfactant independently.In order to the object of this test, use the Ariel brand granular laundry detergent that China is commercially available.Also comprise the contrast of only Ariel laundry detergent.

Then according to the washing foam exponential sum rinsing foam index of testing method test composition described herein.Result is found in table 3.

table 3

Test item	Washing foam index	Rinsing foam index
			Contrast-Chinese Ariel	100％	100％
China Ariel+ example 1	99％	15％
			China Ariel+ comparative example 1	89％	25％

As can in table 3 seen by, according to laundry detergent of the present invention not only show with not containing foam depressant contrast quite or the washing foam index lower than it, also show lower rinsing foam index.The ageing stability of improvement is also shown according to laundry detergent composition of the present invention.

example 2

This example describes the granulating Sudo controlling compositions according to alternative of the present invention.

By at 85 DEG C to describe above the silicone defoamer FC1 of (in example 1) and the tristearin of PAM-MAPTAC solution and nonionogenic tenside and melting carry out mechanically mixing to prepare 4 parts of tristearins, 6 parts of silicone defoamer FC1,0.2 part comprise the solution of the PAM-MAPTAC of 3% and the mixture of 0.2 portion of EO7 nonionogenic tenside.Then, this mixture and extra 8.5 parts of water are poured into simultaneously lentamente on the 81 parts of sodium sulfate existed in mixing machine.This mixture of Keep agitation is until obtain granulated material=example 2.At 65 DEG C, remove with air the water comprised in granulate material in fluidized-bed.

example 3

Prepare 2.9 parts of tristearins, 4.7 parts of first pre-compositions of silicone defoamer FC1 describing (in example 1) above, and make it remain on 85 DEG C.Use high shear mixer to prepare the second pre-composition of the PAM-MAPTAC solution of 7.3 part 6.2% and the active LAS solution of 0.3 part 20%, and make it remain on 85 DEG C.Then use high shear mixer by admixed together for these two kinds of pre-compositions, and in making its granulating in 84.8 parts of anhydrous sodium sulphate subsequently in the horizontal agglomeration machine of high-shear.Then the agglomerate of acquisition is delivered to and is arranged on 50 DEG C have in the fluidized-bed of dry air with except anhydrating.The composition of example 3 is disclosed in table 4.

example 4

Prepare 2.8 parts of tristearins, 4.6 parts of first pre-compositions of silicone defoamer FC1 describing (in example 1) above, and make it remain on 85 DEG C.Use high shear mixer to prepare the second premixture of the PAM-MAPTAC solution of 7.2 part 6.2% and the active LAS solution of 0.3 part 20%, and make it remain on 85 DEG C.Then these two kinds of pre-compositions are delivered to simultaneously comprise in the horizontal high-shear agglomeration machine of 85 parts of anhydrous sodium sulphate.Then the agglomerate of acquisition is delivered to and is arranged on 50 DEG C have in the fluidized-bed of dry air with except anhydrating.The composition of example 4 is disclosed in table 4.

example 5

Prepare 2.7 parts of tristearins, 4.3 parts of first pre-compositions of silicone defoamer FC1 describing (in embodiment 1) above, and make it remain on 85 DEG C.Use high shear mixer to prepare the second premixture of the PAM-MAPTAC solution of 6.8 part 6.2% and the active LAS solution of 0.2 part 20%, and make it remain on 85 DEG C.Then use high shear mixer by admixed together for these two kinds of premixtures, and in making its granulating in 79.6 parts of anhydrous sodium sulphate subsequently in the vertical agglomeration machine of high-shear.Then the agglomerate of acquisition is delivered to and is arranged on 50 DEG C have in the fluidized-bed of dry air.In this fluidized-bed, by comprising 6.4 parts of spray solutions of the PAM-MAPTAC solution of 3 part 6.2%, 3 parts of water and 0.4 portion of C14-15AE7 nonionogenic tenside respectively on obtained particle, then carry out drying.The composition of example 5 is disclosed in table 4.

table 4

Example 3 to 5 (1.5 % by weight) is added into existing comprising in " can be purchased off the shelf " granular laundry detergent composition of anionic detersive surfactant independently.In order to the object of this test, use the Ariel brand granular laundry detergent that China is commercially available.Also comprise the contrast of only Ariel laundry detergent.

Then according to the washing foam exponential sum rinsing foam index of testing method test composition described herein.Result is found in table 5.

table 5

Test item	Washing foam index	Rinsing foam index
			Contrast-Chinese Ariel	100％	100％
China Ariel+ example 3	61％	12％
			China Ariel+ example 4	87％	13％
China Ariel+ example 5	78％	5％

As can in table 5 seen by, not only show lower than the washing foam index of contrast not containing foam depressant according to laundry detergent of the present invention, also show lower rinsing foam index.The ageing stability of improvement is also shown according to laundry detergent composition of the present invention.

Claims (16)

1. a Foam control granules, described Foam control granules comprises

(A) Foam Control, described Foam Control comprises

I () comprises the polydiorganosiloxane fluid of the unit of following formula

Wherein each radicals R can be identical or different, and be selected from the alkyl group with 1-36 carbon atom or have aromatic yl group or the aromatic alkyl group of the most nearly 36 carbon atoms, the average number of the carbon atom in described radicals R is at least 1.3;

(ii) dewatering filling in described polydiorganosiloxane fluid is dispersed in; With

(iii) optional silicone resin;

(B) fusing point is the organic additive comprising polyol ester of 45 DEG C-100 DEG C, described polyol ester is had the polyvalent alcohol of the carboxylate completely or partially esterification of 7-36 carbon atom separately, and miscible with described polydiorganosiloxane fluid (A) (i);

(C) water-soluble granular inorganic carrier;

(D) there is the polymkeric substance of clean cationic charge; And

(E) tensio-active agent.

2. Foam control granules according to claim 1, wherein said Foam control granules comprise by comprise described Foam Control (A), described organic additive (B), described in there is the polymkeric substance (D) of clean cationic charge and described tensio-active agent (E) liquid composition apply and the multiple water-soluble inorganic carrier particles (C) combined by described liquid composition.

3., according to Foam control granules according to claim 1 or claim 2, wherein said to have the polymkeric substance (D) of clean cationic charge and the weight ratio of described tensio-active agent (E) be 1:10 to 100:1.

4. Foam control granules according to any one of claim 1 to 3, wherein said tensio-active agent (E) is selected from nonionogenic tenside, cats product, anion surfactant and zwitterionics, or their mixture.

5. Foam control granules according to any one of claim 1 to 4, wherein said polysiloxane fluid (A) (i) is such polysiloxane, and it comprises: two diorganosiloxane units of the following formula of (a) at least 10%:

Reach most two diorganosiloxane units of the following formula of 90%

Wherein X represents the divalent aliphatic organic group by carbon atom and silicon bonding; Ph represents aromatic group; Y represents the alkyl group with 1-4 carbon atom; And Y' represents the aliphatic hydrocarbon group with 1 to 24 carbon atom; Or (b) two diorganosiloxane units of following formula of 50% to 100%:

With two diorganosiloxane units optionally reaching most the following formula of 50%

Wherein Y represents the alkyl group with 1-4 carbon atom, and Z represents the alkyl group with 6-18 carbon atom.

6. Foam control granules according to any one of claim 1 to 5, the fusing point of the mixture of wherein said organic additive (B) and described polydiorganosiloxane fluid (A) (i) is 45 DEG C to 100 DEG C.

7. Foam control granules according to any one of claim 1 to 6, wherein said polyol ester is by the triglyceride level of the carboxylate esterification completely substantially separately with 14-22 carbon atom.

8. Foam control granules according to any one of claim 1 to 7, wherein said polyol ester is monocarboxylate or the polycarboxylate that wherein said carboxylate has 18 to 22 carbon atoms separately.

9. Foam control granules according to any one of claim 1 to 8, wherein said bead-type substrate is selected from sodium sulfate, sodium carbonate and sodium bicarbonate.

10. Foam control granules according to any one of claim 1 to 9, the wherein said polymkeric substance with clean cationic charge has the net charge density, 80 of 0.05meq/g to 12meq/g, 000 to 4,000, the weight-average molecular weight of 000, and the cationic degree parameter being greater than 50 dalton meq/g as defined herein.

11. Foam control granules according to any one of claim 1 to 10, the wherein said polymkeric substance with clean cationic charge is the addition polymer that (c) cationic polysaccharide or (d) have the synthesis of following formula:

Wherein each R ¹be hydrogen, C independently ₁-C ₁₂alkyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl ,-OR _a, or-C (O) OR _awherein R _abe selected from hydrogen and C ₁-C ₂₄alkyl and their mixing; Each R ²be hydrogen, hydroxyl, halogen, C independently ₁-C ₁₂alkyl ,-OR _a, replace or unsubstituted phenyl, replacement or unsubstituted benzyl, carbocylic radical or heterocyclic radical; And each Z is hydrogen, halogen independently; The C of straight or branched ₁-C ₃₀alkyl, nitrilo ,-N (R ³) ₂-C (O) N (R ³) ₂;-NHCHO (methane amide);-OR ³,-O (CH ₂) _nn (R ³) ₂,-O (CH ₂) _nn ⁺(R ³) ₃x – ,-C (O) OR ⁴;-C (O) N-(R ³) ₂,-C (O) O (CH ₂) _nn (R ³) ₂,-C (O) O (CH ₂) _nn ⁺(R ³) ₃x ^-,-OCO (CH ₂) _nn (R ³) ₂,-OCO (CH ₂) _nn ⁺(R ³) ₃x ^-,-C (O) NH-(CH ₂) _nn (R ³) ₂,-C (O) NH (CH ₂) _nn ⁺(R ³) ₃x ^-,-(CH ₂) _nn (R ³) ₂,-(CH ₂) _nn ⁺(R ³) ₃x ^-, or comprise the quaternized aromatics nitrogen heterocyclic ring of the non-aromatic nitrogen heterocyclic of quaternary ammonium ion, the heterocycle comprising N-oxide portions, one or more nitrogen-atoms; Wherein at least one nitrogen is the aromatics nitrogen heterocyclic ring of N-oxide compound; Each R ₃be hydrogen, C independently ₁-C ₂₄alkyl, C ₂-C ₈the benzyl of hydroxyalkyl, benzyl or replacement; Each R ₄be hydrogen or C independently ₁-C ₂₄alkyl or-(CH ₂-CHR ₅-O) _m-R ³, wherein R ₅be hydrogen or C independently ₁-C ₆alkyl; X is water soluble anion; And n is 1 to 6; Prerequisite is, at least one Z group of per molecule is selected from-O (CH ₂) _nn ⁺(R ³) ₃x ^–,-C (O) OR ⁴;-C (O) N-(R ³) ₂,-C (O) O (CH ₂) _nn (R ³) ₂,-C (O) O (CH ₂) _nn ⁺(R ³) ₃x ^-,-OCO (CH ₂) _nn (R ³) ₂,-OCO (CH ₂) _nn ⁺(R ³) ₃x ^-,-C (O) NH-(CH ₂) _nn (R ³) ₂,-C (O) NH (CH ₂) _nn ⁺(R ³) ₃x ^-,-(CH ₂) _nn (R ³) ₂,-(CH ₂) _nn ⁺(R ³) ₃x ^-, or comprise the quaternized aromatics nitrogen heterocyclic ring of the non-aromatic nitrogen heterocyclic of quaternary ammonium ion, the heterocycle comprising N-oxide portions, one or more nitrogen-atoms; Wherein at least one nitrogen is the aromatics nitrogen heterocyclic ring of N-oxide compound.

12. Foam control granules according to any one of claim 1 to 11, wherein said Foam Control comprises silicone resin (A) (iii), described silicone resin is by formula R " silicone resin that unit price trialkyl siloxy-(M) group of 3SiO1/2 and four senses (Q) group SiO4/2 form; wherein R " represents alkyl group, and M group compares in the scope of 0.4:1 to 1.1:1 with the number of Q group.

13. Foam control granules according to any one of claim 1 to 12, the content of the described polydiorganosiloxane fluid of wherein said Foam control granules presses described Foam control granules weighing scale between 1% and 25%, preferably between 1% and 15%.

14. 1 kinds of Sudo controlling compositions, it comprises the Foam control granules according to any one of claim 1 to 13, the median size of wherein said Sudo controlling compositions is between 150 μm and 700 μm, preferably between 150 μm and 500 μm, most preferably between 200 μm and 500 μm.

15. 1 kinds of methods preparing granulating Sudo controlling compositions, described method comprises:

-mixing

(A) Foam Control, described Foam Control comprises

I () comprises the polydiorganosiloxane fluid of the unit of following formula

Wherein each radicals R can be identical or different, and be selected from the alkyl group with 1-36 carbon atom or have aromatic yl group or the aromatic alkyl group of the most nearly 36 carbon atoms, the average number of the carbon atom in described radicals R is at least 1.3;

(ii) dewatering filling in described polydiorganosiloxane fluid is dispersed in; With

(iii) optional silicone resin; And

(B) fusing point is the organic additive comprising polyol ester of 45 DEG C-100 DEG C, and described polyol ester is had the polyvalent alcohol of the carboxylate completely or partially esterification of 7-36 carbon atom separately; And

-described (A) and the mixture of (B) are deposited on water-soluble granular inorganic carrier, described (A) was non-aqueous liquid form with the mixture of (B) before being deposited on described water-soluble granular inorganic carrier; And

-with the mixture of described (A) and (B) simultaneously or after the mixture of described (A) and (B), the polymkeric substance (D) and tensio-active agent (E) with clean cationic charge are deposited on described water-soluble granular inorganic carrier.

16. methods according to claim 15, wherein before being deposited on described bead-type substrate, the mixture of the polymkeric substance (D) and tensio-active agent (E) with clean cationic charge is mixed with described Foam Control (A) and described organic additive (B).