CN1230520C - Granular detergent compsns. having surfactant particles with reduced electrolyte concentrations - Google Patents
Granular detergent compsns. having surfactant particles with reduced electrolyte concentrations Download PDFInfo
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- CN1230520C CN1230520C CNB008116032A CN00811603A CN1230520C CN 1230520 C CN1230520 C CN 1230520C CN B008116032 A CNB008116032 A CN B008116032A CN 00811603 A CN00811603 A CN 00811603A CN 1230520 C CN1230520 C CN 1230520C
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Abstract
A granular detergent composition is provided in which from about 0.01% to about 60% by weight of the detergent is a surfactant system having an electrolyte rich surfactant zone and a electrolyte poor surfactant zone. The electrolyte rich zone includes an electrolyte and an anionic surfactant which is not an alkyl sulfate surfactant wherein the electrolyte comprises at least about 20% by weight of the electrolyte rich zone. The electrolyte poor zone includes an electrolyte and an alkyl sulfate surfactant wherein the electrolyte comprises less than about 20% by weight of the electrolyte poor zone.
Description
Technical field
The present invention relates to contain the granular detergent composition of the surfactant particles of electrolyte concentration, relate in particular to the detergent composition of the surfactant particles of the carbonate content that contains reduction with reduction.
Background of invention
In recent years, the popular continuous increase of liquid detergent composition, the popular of this growth mainly is owing to compare the superiority of liquid washing agent aspect dispersion and dissolving with its particulate homologue.These dissolvings and dispersive advantage are in the cold water condition, and it is especially tangible promptly being lower than under 30 ℃, and at this moment, the solvency action of traditional detergent granules is insufficient.
Although the advantage of liquid detergent composition, particulate product still keep many advantages.These advantages comprise performance, preparation ability, low-cost packing and higher product stability.The advantage of product stability and preparation ability mainly is because the character of granular mixture produces, each component in the granular mixture with stabilization individually before other particulate mixes, and be separated into particulate.Physical sepn in final detergent composition can be used the material of latent instability in composition, for example SYNTHETIC OPTICAL WHITNER, enzyme etc.
Usually the performance of granular detergent composition depends on the dispersion of particle in washing water and the dissolving of individual particle.Usually have optimum balance between two kinds of character, the particulate of excellent dissolution has poor dissemination usually, and the slowly dissolving usually of the particulate of good distribution.And slowly solvency action is because the quantity of the washing composition that restriction is in the suds influences scourability, and the solvency action that differs from is a undissolved resistates on fabric to the most tangible influence of human consumer.
Although do not plan to be limited to theory, if it is believed that the bridge joint of detergent owner owing to spawn between the surfactant granules, this gel resistates is to produce owing to tensio-active agent is partly dissolved to form high viscosity tensio-active agent paste.Form when this spawn " connection " adjacent microparticle bigger " piece ", in case form, these block gels are difficult to fragmentation, dispersion and dissolving.By the present invention, have now found that the ionogen that in surfactant particles, exists and based on the interaction between the tensio-active agent of alcohol sulfate class because the formation of block gel and in the washing composition combination, be especially problematic, on the other hand, have lower interacting based on the tensio-active agent of alkyl benzyl sulfonic acid salt and form the trend of block gel with ionogen.
Reducing the interactional a kind of method of this ionogen-tensio-active agent is to reduce electrolytical content in the prescription simply, yet, be generally the reduction that this reduction of ionogen (for example yellow soda ash) of alkalescence will produce pH in the washing water, the result reduces the scourability of detergent composition.Therefore, need keep, if can not increase, the electrolyte content in the prescription.
Therefore, the problems of dissolution that still needs to improve around the granular detergent composition surpasses formulation flexibility, the especially solvency action under the cold water condition in the liquid detergent composition to keep it.
Summary of the invention
This demand satisfies by the present invention, wherein the invention provides the granular detergent composition of the surfactant particles that contains the electrolyte content with reduction.The present invention relates to preparation full formula detergent composition in fact, and it contains the surfactant system with rich electrolyte meter surface-active agent zone and poor electrolyte meter surface-active agent zone.Composition can be that the single particulate form with independent discrete surface promoting agent zone maybe can be a plurality of particulate form, and wherein each tensio-active agent zone is by independent particulate representative.In more preferably scheme, poor electrolyte area is agglomerant washing composition particulate, and rich electrolyte area is the spray-dried detergent particulate, and composition also comprises other washing composition auxiliary component.
Poor electrolyte meter surface-active agent zone contain be less than about 20%, more preferably less than about 10%, also preferably be less than about 2%, most preferably from about 0% with tensio-active agent that is selected from the alkyl sulfate surfactant kind or surfactant mixture bonded ionogen.And rich electrolyte meter surface-active agent zone is contained above about 20%, more preferably surpass about 35%, most preferably surpass about 45% and be not alkyl sulfate surfactant with being selected from, be preferably the tensio-active agent or the surfactant mixture bonded ionogen of the anion surfactant of alkylbenzene sulfonate.Therefore, separate through zone of the present invention, wherein ionogen makes the formation of block gel resistates drop to minimum and/or reduction from separating near the alkyl sulfate surfactant, causes the excellent solvency action and the dispersiveness of detergent granules of the present invention.
Therefore, the average tap density that an object of the present invention is to provide excellent properties is at least the granular detergent composition of 450g/L, and it has the solvability curve suitable with liquid washing agent.Another object of the present invention is to separate by the zone of ionogen and some surface active agent composition this solvability is provided.Another object of the present invention provides poor electrolyte area or the particulate that contains alkyl sulfate surfactant and contains the anion surfactant that is not alkyl-sulphate, for example rich electrolyte area of alkyl benzene sulfonate surfactant.To know these and other objects of the present invention, characteristic and advantage by following description and appended claims those skilled in the art.
Detailed description of the preferred embodiments
Definition
The term " particulate " that is used for this paper is meant the overall dimensions scope of washing composition the finished product or component or in final Betengent product or component mixture disperse particles, agglomerate or particulate overall dimensions scope.It is not a size fraction (promptly representing less than 100% overall dimensions scope) of specifically pointing out any of these based fine particles, unless the size fraction is represented in the particle mixture 100% discrete particles.Whether for every type in the mixture particulate constituent, the overall dimensions scope of this class discrete particles has identical or basic similarly composition, contact irrelevant with other particulate with particulate.For the agglomeration component, itself is considered to discrete particles agglomerate, and each discrete particles can be made up of the mixture of less primary fine particles and binder ingredients.The phrase " geometric mean mean particle dia " that is used for this paper is meant the geometry mass mean diameter of one group of discrete particles, with the granular size measuring technology based on quality of any standard, preferably measures by dry sieving." geometric standard deviation " or " span " that is used for the phrase particle size dispersion of this paper is meant the geometric widths to the lognormality function of the best-fit of above-mentioned granular size data, and 84.13% the diameter that it can be by cumulative distribution is divided by the ratio (D of 50% diameter
84.13/ D
50) finish, referring to Gotoh etc., powder technology handbook (Powder Technology Handbook), 6-11 page or leaf, Meral Dekker 1997.
The phrase " washing assistant " that is used for this paper is meant any inorganic substance that have " washing assistant " performance aspect washing, specifically is can be by the organic or inorganic material of removing the water hardness in the washing soln.The term " tap density " that is used for this paper is meant not compacting, the tap density of not patting powder, by pouring the excess powder sample into smooth metal container (for example cylinder of 500 ml volumes) by funnel, scrape off excess powder along pile of grounds from container, measure the residual mass of powder and quality is measured divided by container volume.
The present invention relates to through separation selected detergent granules disperse and dissolution process in the formation that when closer to each other, increases have excellent deliquescent granular detergent composition than the detergent component design of the trend of low-solubility gel.The detergent component that is considered to have the block gel resistates of the formation trend of increase is alkyl sulfate surfactant and ionogen.Ionogen is present in the detergent composition usually to provide such as alkalescence, to help and effect such as wash, and usually as an alkali metal salt, for example carbonate, muriate and vitriol exist, and modal is yellow soda ash, and it is the most preferred ionogen of the present invention.
For utilizing the present invention, detergent granules is divided into poor electrolyte area and rich electrolyte area.The electrolyte content that poor electrolyte area contains is lower than the electrolyte content that exists in the rich electrolyte area.Therefore, alkyl sulfate surfactant is concentrated in poor electrolyte area, is reduced to minimum with electrolytical interaction before thereby tensio-active agent is dissolved fully.Poor electrolyte area contains the electrolyte particulates that is less than about 20% weight, preferably is less than about 10% weight, most preferably is less than the electrolyte particulates of about 2% weight, and about 0 content is most preferred.Poor electrolyte area also preferably includes at least about 2% weight, more preferably from about 5% weight, most preferably from about the alkyl sulfate surfactant particulate of 10% weight.
The electrolyte content that rich electrolyte area contains is than the electrolyte content height that exists in the poor electrolyte area.Therefore, the anion surfactant except that alkyl-sulphate can be formulated into this richness electrolyte area.Anion surfactant alkyl benzene sulfonate surfactant preferably in this zone.Rich electrolyte area contains the electrolyte particulates that surpasses about 20% weight, preferably surpasses about 30% weight, more preferably surpasses the electrolyte particulates of about 35% weight.In addition, rich electrolyte area contains the anionic surfactant particle that surpasses about 0% weight, more preferably surpasses about 2% weight, most preferably surpasses the particulate of 5% weight.
In preferred embodiments, in the time of in allocating detergent granules into, poor electrolyte area and rich electrolyte area comprise the independent particulate of different compositions.Particulate optional from spraying drying, agglomeration, extrude, granulation, compacting and various other particulate preparation method well known in the art.In a preferred embodiment, a kind of particulate can be spray-dired particulate, and another kind of particulate is agglomerant.Preferred rich electrolyte area is a spray-dired particulate and preferred poor electrolyte area is the agglomeration particulate.Certainly, the particulate that those skilled in the art will recognize that other form also can advantageously use.In another embodiment, rich electrolyte area and poor electrolyte area be same particulate separately and different zones, but for example two different independent submicron agglomeration of forming have the single particulate of different zones as described herein together with formation.
Detergent surfactant-
Be used for anion surfactant of the present invention and be divided into the alkyl sulfate surfactant of separating with the ionogen of detergent composition according to the present invention and all the other anion surfactants that can be formulated in arbitrary particulate.The alkyl-sulphate that is used for the object of the invention is defined as alkyl-sulphate, alkyl alkoxy sulfate, alkyl alkoxylated suifate, and remaining anion surfactant is selected from alkylbenzene sulfonate, alhpa olefin sulfonate, alkane sulfonate, alkyl ester sulfonate, sarcosinate, taurate and their mixture.
If exist, anion surfactant will be present in total detergent composition with significant quantity usually, composition more preferably can contain by at least a about 0.5% weight of described composition, more preferably at least about 5% weight, even more preferably at least about the anion surfactant of 10% weight.Composition also will preferably contain by described composition and be no more than about 90% weight, more preferably no more than about 50% weight, even more preferably no more than the anion surfactant of about 30% weight.
Individually and especially providing excellent overall washability when being used in combination with polyhydroxy fatty acid amide (vide infra), be included in the degrease/washing of deoiling good in wide temperature range, wash concentration and the washing time, can obtain the solvency action of alkyl-sulphate and the alkyl sulfate surfactant of the preparation ability improved is formula ROSO in liquid detergent formula
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably contains C
10-C
20The alkyl of alkyl component or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, with M be H or positively charged ion, for example basic metal (IA family) (for example sodium, potassium, lithium) positively charged ion, replacement or unsubstituted ammonium cation, for example methyl-, dimethyl-and trimethyl ammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine and, for example positively charged ion of obtaining of thanomin, diethanolamine, trolamine and their mixture etc. by alkanolamine.Common C
12-C
16Alkyl chain is preferred for low wash temperature (for example being lower than about 50 ℃) and C
16-C
18Alkyl chain is preferred for higher wash temperature (for example being higher than about 50 ℃).
The alkyl sulfate surfactant of another adequate types of the present invention is secondary (2,3) alkyl-sulphate, and these tensio-active agents preferably have following formula:
X and (y+1) be at least about 7 wherein is preferably at least about 9 integer.These tensio-active agents preferably contain 10-18 carbon atom.The suitable example of these anion surfactants is at the US3234258 of the Morris of promulgation on February 8th, 1966; The people's such as Lutz of promulgation on December 24th, 1991 US5075421; Open among the US5389277 of the Prieto of the people's such as Lutz of promulgation on September 20th, 1994 US5349101 and promulgation on February 14 nineteen ninety-five, this paper reference classified as in its each piece of writing.
The alkyl sulfate surfactant of another adequate types of the present invention is an alkyl alkoxylated suifate.These tensio-active agents are formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or contain C
10-C
24The hydroxyalkyl of moieties is preferably C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, are generally about 0.5 to about 6, and more preferably from about 0.5 to about 3, and M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium etc.), ammonium or replacement.The present invention considers alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkanolamine, for example monoethanolamine, diethanolamine, trolamine and their mixture deutero-positively charged ion etc.The tensio-active agent of illustrative is C
12-C
18The many ethoxylations of alkyl (1.0) vitriol, C
12-C
18The many ethoxylations of alkyl (2.25) vitriol, C
12-C
18The many ethoxylations of alkyl (3.0) vitriol and C
12-C
18The many ethoxylations of alkyl (4.0) vitriol, wherein M is selected from sodium and potassium usually.The tensio-active agent that is used for this paper can be by natural or synthol feedstock production.Chain length represents to comprise that the average hydrocarbon of side chain distributes, and the anion surfactant component can contain by conventional alcohol source, and for example natural alcohol, synthol are for example with trade(brand)name NEODOL
TM, ALFOL
TM, LIAL
TMAnd LUTENSOL
TMDeng pure deutero-alkyl-sulphate and the sulfated alkyl ether sold.Sulfated alkyl ether also is called the many ethoxylated sulfates of alkyl.
The alkyl sulfate surfactant of another type of the present invention is one or more (being preferably two or more mixture) mid-chain branched tensio-active agents, is preferably the mid-chain branched alkyl alkoxy alcohol with following formula:
Mid-chain branched alkyl-sulphate with following formula:
With the mid-chain branched alkyl alkoxy sulfate with following formula:
Wherein the total number of carbon atoms (comprises R, R in the branched primary alkyl part of these general formulas
1And R
2Side chain, but be not included in carbon atom in any EO/PO alkoxyl group part) be 14-20, wherein for this surfactant mixture, the average the total number of carbon atoms in the branched primary alkyl in above-mentioned general formula is to about 17.5 (preferably about 15-about 17) greater than 14.5; R, R
1And R
2Be independently selected from H, C respectively
1-C
3Alkyl and their mixture are preferably methyl; Its condition is R, R
1And R
2All not hydrogen and when z is 1, R or R at least
1Not hydrogen.M is a water-soluble cationic, can contain to surpass one type positively charged ion, for example mixture of sodium and potassium.Coefficient w is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is at least 1 integer; Its condition is that w+x+y+z is 8-14, and EO and PO represent the ethylene oxy unit and have the propylene oxygen unit of following formula:
Yet, other oxyalkyl units, especially 1, the also suitable oxyalkyl units of 3-propylene oxygen, butoxy and their mixture as the mid-chain branched moieties.
The mid-chain branched tensio-active agent preferably contains the mixture of surfactant system, therefore, when surfactant system contains alkoxy-based surface-active agent, oxyalkylated average degree in the Coefficient m presentation surface active agent intermixture.Thus, Coefficient m is at least about 0.01, preferably from about 0.1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably to about 5.When considering only to contain the mid-chain branched surfactant system of alkoxy-based surface-active agent, the numeric representation of Coefficient m is corresponding to the distribution of the alkoxylate average degree of m, or it can be to have the single concrete chain of the alkoxylate of cut unit numerical value (for example ethoxylation and/or propoxylation) really corresponding to m.
The of the present invention preferred mid-chain branched tensio-active agent that is suitable for surfactant system of the present invention has following formula:
Wherein a, b, d and e are that integer makes that a+b is that 10-16 and d+e are 8-14; M is selected from the ammonium of sodium, potassium, magnesium, ammonium and replacement and their mixture.
The surfactant system of the present invention that contains the mid-chain branched tensio-active agent is preferably prepared in two kinds of embodiments.First preferred embodiment comprises the mid-chain branched tensio-active agent, they by contain 25% or the raw material of following mid-chain branched alkyl unit form.Therefore, with before any other conventional surfactants is mixed, the mid-chain branched surface active agent composition will contain 25% or following be the surfactant molecule of nonlinear surface promoting agent.
Second preferred embodiment comprises the mid-chain branched tensio-active agent, they are that raw material by the mid-chain branched alkyl unit that contains the 25%-that has an appointment about 70% forms, therefore, with before any other conventional surfactants is mixed, what the mid-chain branched surface active agent composition will contain the 25%-that has an appointment about 70% is the surfactant molecule of nonlinear surface promoting agent.
These tensio-active agents are further at the US patent application № 60/061971 on October 14th, 1997, attorney docket numbering 6881P, the № 60/061975 on October 14th, 1997, attorney docket numbering 6882P, the № 60/062086 on October 14th, 1997, attorney docket numbering 6883P, the № 60/061916 on October 14th, 1997, attorney docket numbering 6884P, the № 60/061970 on October 14th, 1997, attorney docket numbering 6885P, the № 60/062407 on October 14th, 1997, describe among the attorney docket numbering 6886P, other suitable mid-chain branched tensio-active agent can be at US patent application series № 60/032035 (attorney docket numbering 6401P), 60/031845 (attorney docket numbering 6402P), 60/031916 (attorney docket numbering 6403P), 60/031917 (attorney docket numbering 6404P), 60/031761 (attorney docket numbering 6405P), 60/031762 (attorney docket numbering 6406P) and 60/031844 (attorney docket numbering 6409P).The mixture of these branched chain surfactants and conventional linear surface promoting agent also is applicable to composition of the present invention.
In the anion surfactant of the present invention in not being included in alkyl-sulphate of the present invention, the operable anion surfactant of a class comprises alkyl ester sulfonate.They are desirable because they can enough reproducible non-petroleum sources preparations.The preparation of alkyl sulfonate surfactants component can be carried out according to disclosed currently known methods in the technical literature.For example, according to " american petroleum chemist association will " (" The Journal of the AmericanOil Chemists Soci ety ") 52 (1975), 323-329 page or leaf, C
8-C
20The linear ester of carboxylic acid can be used gaseous state SO
3Sulfonation.Suitable starting material can comprise the natural fat material that is obtained by butter, plam oil and coconut wet goods.
The preferred alkyl sulfonated ester tensio-active agent that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:
R wherein
3Be C
8-C
20Alkyl is preferably alkyl or their combination, R
4Be C
1-C
6Alkyl, being preferably alkyl or their combination and M is water-soluble salt-forming cation.Suitable salt comprises metal-salt, for example sodium salt, sylvite and lithium salts, with replacement or unsubstituting ammonium salt, for example methyl-, dimethyl, trimethylammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine and by alkanolamine, for example monoethanolamine, diethanolamine and trolamine deutero-positively charged ion.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl, especially preferable methyl sulfonated ester, wherein R
3Be C
14-C
16Alkyl.
The anion surfactant of operable another type is an alkylbenzene sulfonate.They comprise firmly (ABS, TPBS), straight chain type, are also referred to as LAS, by currently known methods preparation, and for example various HF or solid HF, for example DETAL (UOP) method or by using other lewis acid catalyst, for example AlCl
3Preparation or use acid silicon dioxide/aluminum oxide prepare or are prepared by hydrochloric ether, for example C
9-C
20Linear alkylbenzene sulfonate, especially straight chained alkyl C
10-C
15Benzene sulfonic acid sodium salt.These tensio-active agents are formula RASO
3The water-soluble salt of M or acid, wherein R is side chain or straight chain C
10-C
24Alkyl is preferably C
10-C
20Alkyl, more preferably C
10-C
18Alkyl, A are aryl, are preferably benzene or toluene, benzene unit more preferably, and M is H or positively charged ion, it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium etc.), ammonium or replacement for example.
The surfactant system of laundry detergent composition of the present invention also comprises by surfactant system from about 0.001% weight, preferably from about 1% weight, more preferably from about 5% weight, most preferably from about 10% weight to about 100% weight, preferably to about 60% weight, more preferably to one or more (preferably two or more the mixture) modified alkylaryl sulfonate surfactants or the preferred MLAS tensio-active agent of about 30% weight, wherein aryl unit is the phenyl ring with following formula:
Wherein L is the acyclic hydrocarbon group part that contains 6-18 carbon atom; R
1, R
2And R
3Be respectively H or C independently
1-C
3Alkyl, its condition is R
1And R
2Be not connected the unitary end of L; M is the water-soluble cationic with electric charge q, and wherein a and b satisfy neutral charge together.
These and other suitable MLAS tensio-active agent is not further being examined US patent application № 60/053319 jointly, attorney docket № 6766P, and on July 21st, 1997 submitted to; № 60/053318, attorney docket № 6767P, and on July 21st, 1997 submitted to; № 60/053321, attorney docket № 6768P, and on July 21st, 1997 submitted to; № 60/053209, attorney docket № 6769P, and on July 21st, 1997 submitted to; № 60/053328, attorney docket № 6770P, and on July 21st, 1997 submitted to; № 60/053186, attorney docket № 6771P, and on July 21st, 1997 submitted to; № 60/105017, attorney docket № 7303P, and on October 20th, 1998 submitted to; № 60/104962, attorney docket № 7304P, and on October 20th, 1998 submitted to and № 60/144519, and attorney docket № 7663P describes in submitting on June 19th, 1999.The mixture of these modified surface promoting agents and conventional surfactants and/or branched chain surfactant (for example as herein described) also is applicable in the present composition.
The example of suitable anion tensio-active agent provides in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).Also general description is at the US3929678 of the Laughlin of on December 30th, 1975 promulgation etc. for various these class tensio-active agents, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row.
Other anion surfactant that is used for washing purposes also can be included in the present composition.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C
8-C
22Uncle or secondary sulfonated alkane, C
8-C
24Alkene sulfonate; the sulfonation poly carboxylic acid that the sulfonation reaction of the split product of describing in british patent specification 1082179 for example that pass through alkaline earth metal citrate prepares; alkyl glycerol sulfonate; the fatty acyl group glycerol sulfonate; fatty oil base glycerol vitriol; alkylphenol oxyethane ether sulfate; paraffin sulfonate; alkylphosphonic; different thiosulphate; for example, the different thiosulphate of acyl group; the N-acyl taurine salt; the fatty acid amide of methyl tauride; alkyl succinate and sulfosuccinate; sulfosuccinic acid monoesters (especially saturated and unsaturated C
12-C
18Monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C
6-C
14Diester), the vitriol of N-acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (hereinafter describing the compound of nonionic non-sulfuric acidization) for example, chain primary alkyl sulfate, the many ethoxy carboxylates of alkyl, for example molecular formula is RO (CH
2CH
2O)
k-CH
2COO
-M
+The many ethoxy carboxylates of alkyl, wherein R is C
8-C
22Alkyl, k are the 0-10 integers, and M is a water miscible salt-forming cation and with the isethionic acid esterification with sodium hydroxide neutral lipid acid.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and be present in or by Yatall MA deutero-resinous acid and hydrogenated resin acid.Other example provides in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).Also general description is at the people's such as Laughlin of promulgation on December 30th, 1975 US3929678 for various these class tensio-active agents, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row.
Another kind of useful anion surfactant is so-called two anionic species.They are the tensio-active agents that have at least two anionic groups in surfactant molecule.Some two suitable anion surfactant is at the common US series № 60/020503 (files № 6160P) that does not examine of application on June 28th, 1996, № 60/020772 (files № 6161P), № 60/020928 (files № 6158P), the № 60/023539 (files № 6192P) of № 60/020832 (files № 6159P) and № 60/020773 (files № 6162P) and application on August 8th, 1996, № 60/023493 (files № 6194P), further describe among № 60/023540 (files № 6193P) and the № 60/023527 (files № 6195P), its content is classified this paper reference as.
Detergent component
Detergent composition can and preferably include detergent builders.Washing assistant is selected from phosphoric acid salt, polyphosphate, phosphonate, polyphosphonic acid salt, carbonate, silicate, borate, polyhydroxy sulfonate, polyacetic acid salt, carboxylate salt and the multi-carboxylate of the ammonium of various water-soluble alkalis, ammonium or replacement usually.Preferably above-mentioned an alkali metal salt, especially sodium salt.Being preferred for of the present invention is phosphoric acid salt, carbonate, silicate, C
10-18Lipid acid, multi-carboxylate and their mixture.Most preferably be tripoly phosphate sodium STPP, tetrasodium pyrophosphate, Citrate trianion, tartrate list and disuccinate, water glass and their mixture (vide infra).
The specific examples of inorganic phosphate builders is that tri-polyphosphate, pyrophosphate salt, the polymerization degree of sodium and potassium is polymer metaphosphate and the orthophosphoric acid salt of about 6-21.The example of polyphosphonic acid salt washing assistant is the sodium of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1, the sodium salt of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane, 1,1, the sodium salt of 2-tri methylene phosphonic acid and sylvite.Other phosphorous washing-aid compound is open in US3159581,3213030,3422021,3422137,3400176 and 3400148, all classifies this paper reference as.
The example of non-phosphorus, inorganic builders is that the weight ratio of carbonate, supercarbonate, sesquicarbonate, tetraborate decahydrate and silicon-dioxide and alkalimetal oxide of sodium and potassium is about 4.0 for about 0.5-, the silicate of preferably about 1.0-about 2.4.The water-soluble non-phosphorus organic washing-assisting detergent that is used for this paper comprises polyacetic acid salt, carboxylate salt, multi-carboxylate and the polyhydroxy sulfonate of various basic metal, ammonium and replacement ammonium.Polyacetic acid salt and multi-carboxy acid salt washing agent's example is sodium salt, sylvite, lithium salts, ammonium salt and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxo disuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.
Multi-carboxylate polymer's washing assistant illustrates that its disclosure is classified this paper reference as in the US3308067 of the Diehl of promulgation on March 7th, 1967.This material comprises aliphatic carboxylic acid, for example the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, aconic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.This material of part is as hereinafter described water-soluble anionic polymer, but only be with the dense mixture of non-soap anionic surfactant in.
Other the suitable multi-carboxylate who is used for this paper is the polyacetal carboxylation who describes at the US4246495 of the US4144226 of the Crutchfield of on March 13rd, 1979 promulgation etc. and the Crutchfield of promulgation on March 27th, 1979 etc., and two pieces of patents are classified this paper reference as.These polyacetal carboxylations can mix preparation by make the ester of oxoethanoic acid and polymerization starter under polymerizing condition.The polyacetal carboxylic acid ester who obtains is connected with chemically stable end group subsequently stablizing the polyacetal carboxylic acid ester preventing that in basic solution depolymerization is converted into corresponding salt rapidly, and joins in the detergent composition.Especially preferred polycarboxylate washing assistant is the ether carboxylate lotion-aid combination that contains tartrate monosuccinic acid ester and tartrate disuccinic acid ester binding substances, described in the US4663071 of the Bush of on May 5th, 1987 promulgation etc., its content is classified this paper reference as.
By formula SiO
2M
2The water-soluble silicate solid that O represents is a salt useful in detergent particles of the present invention, and wherein M is a basic metal, SiO
2: M
2The O weight ratio is about 4.0 for about 0.5-, and it is benchmark with the moisture free weight, and content is that about 2%-is about 15%, preferably about 3%-about 8%.
Many supplementary components also can be used as component and are included in the granular detergent composition.They comprise other detergent builder compound, SYNTHETIC OPTICAL WHITNER, bleach activator, suds booster or suds suppressor, anti-dark and gloomy and sanitas, soil-suspending agent, stain remover, sterilant, pH regulator agent, non-washing assistant alkaline source, sequestrant, smectic clays, enzyme, enzyme stabilizers and spices.Referring to the Baskerville of promulgation on February 3rd, 1976, the US3936537 of Jr. etc. classifies this paper reference as.
Describe among the US4483781 of the Hartman of the US4412934 of the Chung that SYNTHETIC OPTICAL WHITNER and bleach activator were issued in November 1 nineteen eighty-three etc. and promulgation on November 20th, 1984, all classify this paper reference as.Sequestrant also at the US4663071 of Bush etc., describe in the 18th hurdle 68 row, classifies this paper reference as by the 17th hurdle 54 row.Foam properties-correcting agent also is the component of choosing wantonly, the US3933672 of the Bartoletta of on January 20th, 1976 promulgation etc. and the Gault of promulgation on January 23rd, 1979 etc. 4136045 in describe, all classify this paper reference as.
The suitable smectic clays that is used for this paper walks to the 7th hurdle the 24th row on the 6th hurdle the 3rd of the US4762645 of the Tucker of promulgation on August 9th, 1988 etc. and describes, and classifies this paper reference as.The suitable additional detergent builder compound that is used for this paper walks to the 16th hurdle 16 row and enumerates at the US4663071 of the Bush of promulgation on May 5th, 1987 etc. on Baskerville patent the 13rd hurdle 54, classify this paper reference as.
Following embodiment only is used to illustrate, and constitutes the restriction to the scope of claim never in any form.
The abbreviation of Shi Yonging in an embodiment
In detergent composition, the component of abbreviation symbol has following implication:
LAS: straight chain C
11-13Sodium alkyl benzene sulfonate
TAS: tallow alkyl sodium sulfate
C45AS: C
14-C
15Sodium alkyl sulfate
C45E3S: with the C of 3 moles of ethylene oxide condensations
14-C
15Sodium alkyl sulfate
QAS ：R
2.N
+(CH
3)
2(C
2H
4OH)，R
2＝C
12-C
14
Soap: the straight chained alkyl that obtains by butter and coco-nut oil fatty acid 80/20 mixture
Carboxylic acid sodium
Zeolite A: formula Na
12(AlO
2SiO
2)
1227H
2The hydrated sodium aluminosilicate of O, main
Grain size is 0.1-10 micron (weight of representing based on anhydrous benchmark)
NaSKS-6: formula 6-Na
2Si
2O
5Crystalline layered silicate
Citric acid: Citric Acid, usp, Anhydrous Powder
Carbonate: anhydrous sodium carbonate, 200 microns-900 microns of granular sizes
Supercarbonate: anhydrous sodium bicarbonate, particle size dispersion are 400 microns-1200 microns
Silicate: amorphous sodium silicate (SiO
2: Na
2O=2.0: 1)
Vitriol: anhydrous sodium sulphate
Sal epsom: anhydrous magnesium sulfate
Citrate trianion: citrate trisodium dihydrate, activity 86.4%, particle size dispersion 425
-850 microns of microns
MA/AA: 1:4 toxilic acid/acrylic copolymer, molecular-weight average about 70000
AA: molecular-weight average is 4500 polyacrylic acid sodium polymer
CMC: Xylo-Mucine
Proteolytic enzyme: protease, contain the organized enzyme of 4% weight, as WO95/10591
Described in, sell by Genencor Int.Inc.
Cellulase: cellulolytic enzyme, contain the organized enzyme of 0.23% weight, by NOVO
Industries A/S sells with trade(brand)name Carezyme
Amylase: amylolytic enzyme, contain the organized enzyme of 1.6% weight, by NOVO
Industries A/S sells with trade(brand)name Termamyl 120T
Lipase: lipolytic enzyme, contain the organized enzyme of 2.0% weight, by NOVO
Industries A/S sells with trade(brand)name Lipolase
Perborate: Sodium peroxoborate
Percarbonate: SPC-D
NOBS: the nonanoly acyloxy benzene sulfonate of sodium-salt form
NAC-OBS: (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate
TAED: tetra acetyl ethylene diamine
DTPA: diethylenetriamine pentaacetic acid
EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer of sodium-salt form
Photoactivation: the sulfonation zinc phthalocyanine phthalocyanine of in SYNTHETIC OPTICAL WHITNER (1) dextrin dissolved polymers, sealing
Whitening agent: 4,4 '-two (4-anilinos-6-morpholine-1,3,5-triazines-2-
Base) Stilbene-2.2 '-disulfonic acid disodium amino)
HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid
PEGx: polyoxyethylene glycol, molecular weight x (common 4000)
QEA: two ((C
2H
5O) (C
2H
4O)
n) (CH
3)-N
+-C
6H
12-N
+-(CH
3)
Two ((C
2H
5O)-(C
2H
4O))
n, n=20-30 wherein
SRP: diethoxyization is gathered (phthalic acid 1,2-propylene glycol ester) short chain embedding
The section polymkeric substance
Polysiloxane: with siloxanes-oxyalkylene copolymers is the polydimethylsiloxane of dispersion agent
The defoamer Foam Control, the ratio of described Foam Control and described dispersion agent is
10∶1-100∶1
In following embodiment, all content use the weight % by composition to represent.
Embodiment 1
Following composition is according to of the present invention.
| A | B | C | D | E | F | G | H | I | |
| Spray-dried granules | |||||||||
| LAS | 10.0 | 10.0 | 15.0 | 5.0 | 5.0 | 10.0 | - | - | - |
| QAS | 1.0 | 1.0 | - | - | - | ||||
| DTPA, HEDP and/or EDDS | 0.3 | 0.3 | 0.5 | 0.3 | - | - | - | ||
| MgSO4 | 0.5 | 0.5 | 0.1 | - | - | - | - | ||
| Trisodium Citrate | - | - | - | 3.0 | 5.0 | - | - | - | |
| Yellow soda ash | 10.0 | 10 | 15 | 10 | 7 | 10 | - | - | - |
| Sodium sulfate | 5.0 | 5.0 | - | - | 5.0 | 3.0 | - | - | - |
| Water glass 1.6R | - | - | - | - | 2.0 | - | - | - | |
| Zeolite A | 16.0 | 18.0 | 20.0 | 20.0 | - | - | - | - | - |
| SKS-6 | - | - | - | 3.0 | 5.0 | - | - | - | - |
| MA/AAorAA | 1.0 | 2.0 | 11.0 | - | - | 2.0 | - | - | - |
| PEG4000 | - | 2.0 | - | 1.0 | - | 1.0 | - | - | - |
| QEA | 1.0 | - | - | - | 1.0 | - | - | - | - |
| Whitening agent | 0.05 | 0.05 | 0.05 | - | 0.05 | - | - | - | - |
| Silicone oil | 0.01 | 0.01 | 0.01 | - | - | 0.01 | - | - | - |
| - | |||||||||
| Agglomerate | - | ||||||||
| LAS | - | - | - | - | 0.2 | 0.2 | 0.01 | ||
| C 45AS | - | - | - | - | 2.0 | - | 1.0 | ||
| AE 3 | - | - | - | - | - | 1.0 | 0.5 | ||
| Carbonate | - | - | 4.0 | 1.0 | 1.0 | 1.0 | - | ||
| Trisodium Citrate | - | - | - | - | - | - | 5.0 | ||
| - | - | - | - | - | |||||
| Citric acid | - | - | - | 4.0 | - | 1.0 | 1.0 | ||
| QEA | - | - | - | 2.0 | 2.0 | 1.0 | - | ||
| SRP | - | - | - | 1.0 | 1.0 | 0.2 | - |
| Zeolite A | - | - | - | 15.0 | 26.0 | 15.0 | 16.0 | ||
| Water glass | - | - | - | - | - | - | - | ||
| PEG | - | - | - | - | - | - | 4.0 | - | - |
| Builder agglomerates | |||||||||
| SKS-6 | 6.0 | - | - | - | 6.0 | 3.0 | - | 7.0 | 10.0 |
| LAS | 4.0 | 5.0 | - | - | 5.0 | 3.0 | - | 10.0 | 12.0 |
| The dried particulate constituent that adds | |||||||||
| Toxilic acid/carbonate | 8.0 | - | 10.0 | 4.0 | - | 8.0 | - | - | 4.0 |
| (40∶20∶40) | |||||||||
| QEA | - | - | - | 0.2 | 0.5 | - | - | - | - |
| NACAOBS | 3.0 | - | - | 1.5 | - | - | - | 2.5 | - |
| NOBS | - | 3.0 | 3.0 | - | - | - | - | - | 5.0 |
| TAED | 2.5 | - | - | 1.5 | 2.5 | 6.5 | - | 1.5 | - |
| LAS (sheet) | 10.0 | 10.0 | - | - | - | - | - | 8.0 | - |
| Spray | |||||||||
| Whitening agent | 0.2 | 0.2 | 0.3 | 0.1 | 0.2 | 0.1 | - | 0.6 | - |
| Dyestuff | - | - | - | 0.3 | 0.05 | 0.1 | - | - | - |
| AE7 | - | - | - | - | - | 0.5 | - | 0.7 | - |
| Spices | - | - | - | 0.8 | - | 0.5 | - | 0.5 | - |
| Dried adding | |||||||||
| Citrate trianion | - | - | 20.0 | 4.0 | - | 5.0 | 15.0 | - | 5.0 |
| Percarbonate | 15.0 | 3.0 | 6.0 | 10.0 | - | - | - | 18.0 | 5.0 |
| Perborate | - | - | - | - | 6.0 | 8.0 | - | - | - |
| Optical white | 0.02 | 0.02 | 0.02 | 0.1 | 0.05 | - | 0.3 | - | 0.03 |
| Enzyme (cellulase, amylase, proteolytic enzyme, lipase) | 1.3 | 0.3 | 0.5 | 0.5 | 0.8 | 2.0 | 0.5 | 0.16 | 0.2 |
| Carbonate | 0.0 | 10.0 | - | - | - | 5.0 | 8.0 | 10.0 | 5.0 |
| Spices (sealing) | 0.6 | 0.5 | 0.5 | - | 0.3 | 0.5 | 0.2 | 0.1 | 0.6 |
| Suds suppressor | 1.0 | 0.6 | 0.3 | - | 0.10 | 0.5 | 1.0 | 0.3 | 1.2 |
| Soap | 0.5 | 0.2 | 0.3 | 3.0 | 0.5 | - | - | 0.3 | - |
| Citric acid | - | - | - | 6.0 | 6.0 | - | - | - | 5.0 |
| Dyeing carbonate (indigo plant, green) | 0.5 | 0.5 | 1.0 | 2.0 | - | 0.5 | 0.5 | 0.5 | 1.0 |
| SKS-6 | - | - | - | 4.0 | - | - | - | 6.0 | - |
| Filler adds to 100% |
The geometric mean mean particle dia that the above-mentioned composition of enumerating contains at least 90% weight is about 850 microns, and geometric standard deviation is about 1.2 particulate, and unexpectedly, said composition has been improved aesthetic property, flowability and solvability.
As above describe the present invention in detail, for a person skilled in the art, obviously can carry out various changes and without prejudice to scope of the present invention, the present invention does not think and is limited to the described content of specification sheets.
Claims (6)
1. an average tap density is at least the granular detergent composition of 450g/L, it is characterized in that:
I) spraying drying surfactant particles, wherein said particulate are characterised in that by the alkyl benzene sulfonate surfactant of dispersimeter 2% weight with by the ionogen of described dispersimeter 20% weight at least at least; With
Ii) agglomeration surfactant particles, wherein said particulate are characterised in that by the alkyl sulfate surfactant of dispersimeter at least 2% weight and are less than the ionogen of 2% weight.
2. the detergent composition of claim 1 is at least 35% weight of described particulate at ionogen described in the described spraying drying surfactant particles wherein.
3. one of any detergent composition of claim 1-2, wherein said alkyl sulfate surfactant is selected from C
14-C
15The alkylsurfuric acid salt mixture.
4. one of any detergent composition of claim 1-2, wherein said alkyl benzene sulfonate surfactant is selected from C
11-C
13Alkyl benzene sulfonate surfactant.
5. one of any detergent composition of claim 1-2, wherein said ionogen is an an alkali metal salt.
6. one of any detergent composition of claim 1-2, wherein said ionogen is an alkaline carbonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14804999P | 1999-08-10 | 1999-08-10 | |
| US60/148,049 | 1999-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1370223A CN1370223A (en) | 2002-09-18 |
| CN1230520C true CN1230520C (en) | 2005-12-07 |
Family
ID=22524018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008116032A Expired - Fee Related CN1230520C (en) | 1999-08-10 | 2000-08-07 | Granular detergent compsns. having surfactant particles with reduced electrolyte concentrations |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP1204736A1 (en) |
| JP (1) | JP2003506564A (en) |
| KR (1) | KR100462265B1 (en) |
| CN (1) | CN1230520C (en) |
| AR (1) | AR025083A1 (en) |
| AU (1) | AU777235B2 (en) |
| BR (1) | BR0013082A (en) |
| CA (1) | CA2380327A1 (en) |
| CZ (1) | CZ2002451A3 (en) |
| EG (1) | EG22449A (en) |
| HU (1) | HUP0202875A3 (en) |
| MA (1) | MA25541A1 (en) |
| MX (1) | MXPA02001515A (en) |
| TR (1) | TR200200329T2 (en) |
| WO (1) | WO2001011005A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1754779B1 (en) * | 2005-08-19 | 2012-10-17 | The Procter and Gamble Company | A solid laundry detergent composition comprising anionic detersive surfactant and a highly porous carrier material |
| JP6407682B2 (en) * | 2014-11-27 | 2018-10-17 | 花王株式会社 | Method for producing powder detergent composition for clothing |
| CN111201310B (en) * | 2017-10-19 | 2021-08-06 | 宝洁公司 | Cleaning compositions comprising fatty acid blends |
| US11499124B2 (en) * | 2020-03-13 | 2022-11-15 | YFY Consumer Products, Co. | Solid granules used for cleaning agents |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ9594A3 (en) * | 1991-07-15 | 1994-06-15 | Procter & Gamble | Process for preparing detergent composition containing alkyl sulfate particles and base granules |
| DE19519139A1 (en) * | 1995-05-30 | 1996-12-05 | Henkel Kgaa | Granular detergent or cleaning agent with high bulk density |
| DE69825487T2 (en) * | 1998-01-13 | 2005-08-18 | The Procter & Gamble Company, Cincinnati | GRANULAR COMPOSITIONS WITH IMPROVED RESOLUTION |
-
2000
- 2000-08-07 HU HU0202875A patent/HUP0202875A3/en not_active Application Discontinuation
- 2000-08-07 BR BR0013082-6A patent/BR0013082A/en not_active Application Discontinuation
- 2000-08-07 EP EP00953859A patent/EP1204736A1/en not_active Withdrawn
- 2000-08-07 TR TR2002/00329T patent/TR200200329T2/en unknown
- 2000-08-07 WO PCT/US2000/021484 patent/WO2001011005A1/en not_active Application Discontinuation
- 2000-08-07 CN CNB008116032A patent/CN1230520C/en not_active Expired - Fee Related
- 2000-08-07 MX MXPA02001515A patent/MXPA02001515A/en unknown
- 2000-08-07 CA CA002380327A patent/CA2380327A1/en not_active Abandoned
- 2000-08-07 AU AU66236/00A patent/AU777235B2/en not_active Ceased
- 2000-08-07 KR KR10-2002-7001751A patent/KR100462265B1/en not_active IP Right Cessation
- 2000-08-07 JP JP2001515794A patent/JP2003506564A/en not_active Withdrawn
- 2000-08-07 CZ CZ2002451A patent/CZ2002451A3/en unknown
- 2000-08-09 AR ARP000104109A patent/AR025083A1/en unknown
- 2000-08-12 EG EG20001049A patent/EG22449A/en active
-
2002
- 2002-02-08 MA MA26517A patent/MA25541A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU777235B2 (en) | 2004-10-07 |
| HUP0202875A2 (en) | 2002-12-28 |
| KR100462265B1 (en) | 2004-12-17 |
| HUP0202875A3 (en) | 2005-01-28 |
| CZ2002451A3 (en) | 2002-09-11 |
| CA2380327A1 (en) | 2001-02-15 |
| CN1370223A (en) | 2002-09-18 |
| WO2001011005A1 (en) | 2001-02-15 |
| MXPA02001515A (en) | 2002-07-02 |
| BR0013082A (en) | 2002-04-23 |
| AU6623600A (en) | 2001-03-05 |
| KR20020016004A (en) | 2002-03-02 |
| EG22449A (en) | 2003-02-26 |
| AR025083A1 (en) | 2002-11-06 |
| JP2003506564A (en) | 2003-02-18 |
| TR200200329T2 (en) | 2002-07-22 |
| MA25541A1 (en) | 2002-10-01 |
| EP1204736A1 (en) | 2002-05-15 |
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