CN1192775A - Pigmented rheopectic cleaning compositions with thioxotropic properties - Google Patents

Pigmented rheopectic cleaning compositions with thioxotropic properties Download PDF

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CN1192775A
CN1192775A CN96196185A CN96196185A CN1192775A CN 1192775 A CN1192775 A CN 1192775A CN 96196185 A CN96196185 A CN 96196185A CN 96196185 A CN96196185 A CN 96196185A CN 1192775 A CN1192775 A CN 1192775A
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sodium
hypochlorite
amine oxide
composition
alkyl
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CN96196185A
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CN1102649C (en
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戴维·A·张
詹姆斯·W·卡瓦纳
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Reckitt Benckiser LLC
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Reckitt and Colman Inc
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Priority claimed from GB9516372A external-priority patent/GB2304113B/en
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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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Abstract

A pigmented bleach-containing hard surface cleaner comprises an alkali metal hypochlorite, bentonite clay, a mono-(long chain alkyl)-tertiary amine oxide, an alkali metal salt, a pH stabilizer to attain a pH of 11 or higher, an alkali metal alkyl sarcosinate, an alkylbenzene sulphonate, and an inorganic pigment which is preferably ultramarine blue. The cleaning composition has excellent colour stability as well as phase stability and hypochlorite stability.

Description

Coloured stream with thixotropic nature coagulates cleaning compositions
Invention field
The present invention relates to be used for the thick liquid composition that comprises SYNTHETIC OPTICAL WHITNER of hard-surface cleaning, relate to comprise the composition of the pigment of bleach stable more specifically.
Background of invention
The thickness bleaching composition has more advantage than non-heavy-gravity bleaching composition.Compare mutually more tacky, thicker liquid can stick to vertical and the surface that tilts on the longer time, the antimicrobial activity of viscous composition uses regional effect bigger to institute in other words.
For making the thickness hypochlorite compositions have acceptable preservation period, just must consider alkaline metal hypochlorite's the rate of decomposition and the phase behaviour of said composition.Know as known, alkaline metal hypochlorite's degraded can be represented by following balanced type:
Therefore many conventional thickening materials have quickened the degraded of hypochlorite, a difficult problem are arranged being used for hypochlorite compositions.Equally, it also is difficult adding conventional thickening material and tensio-active agent, and this is because the gained hypochlorite compositions can be separated into two-phase or more heterogeneous, and is particularly like this when high temperature.This also is unsettled when having the alkaline metal hypochlorite for many thickening materials.So, be difficult to make hypochlorite compositions reach enough viscosity, and make hypochlorite compositions have acceptable stability by conventional reagent and additive.
From commercial and aesthetic perspective, still be desirable to provide the viscous composition that comprises SYNTHETIC OPTICAL WHITNER and have obvious color.The pigment of bleach stable seldom, this be because pigment dyestuff when strong oxidizer exists, can degrade.
United States Patent (USP) 4,474,677 (Foxlee) propose to use some copper halide phthalocyanine pigment in aqueous alkaline metal hypochlorite's composition.Though considering such pigment is bleach stable, the slow degraded of pigment molecule discharges copper, but the degraded of its catalysis hypochlorite.United States Patent (USP) 4,271,030 (Brierley) have been described a kind of ultramarine suspension that uses the calcium soap flocculation agent.The use of calcium soap flocculation agent is undesirable, and this is because concentration requirement is higher, need reach 50 volume % of composition, perhaps sees and can produce precipitation at crust from the cleaning angle.United States Patent (USP) 4,952,333 (Cramer) have been described the bleaching lightening composition that uses polymkeric substance, so that ultramarine is suspended in the Emulgating polymers matrix.But said composition is because its soil release characteristics difference and invalid to crust.United States Patent (USP) 4,917,814 (MacIntyre) have described the use Leyden blue, with dyeing heavy-gravity hypochlorite solutions.See that from suspension property cobalt pigment is better than ultramarine.Though do not discuss at this, be to be noted that the tensio-active agent viscous composition will lose viscosity, and make the pigment sedimentation under the temperature higher than temperature that MacIntyre adopted.Between transportation and shelf lives, the stability that the finished product need be when being exposed to these higher temperature.
Summary of the invention
The invention provides thickness hypochlorite compositions, the said composition mineral dye that can stably suspend with enhanced rheological property.This viscous systems is the blend of tensio-active agent and clay, described clay is a rheological under low shear rate, and it helps stable suspersion pigment, but then is thixotropic when high shear rate more, make product to help cleaning of hard surfaces easily by distributing in the container.From definition, rheological and thixotropy are opposite flowing properties.It is quite favourable having these two kinds of character in a fluid simultaneously.
The non-limitative example of spendable mineral dye comprises ultramarine, aluminic acid cobalt blue, titanium dioxide and lime carbonate.The present invention mainly is to use ultramarine, and why preferably it is because it compares to client's attractability, hypotoxicity and the colour density of other pigment.
The performance of said composition is as attach structure liquid, and has unique and be unexpected flowing property.Compare with other structured liquids,, also can have these character even when low solid content, be lower than 10% of composition.Known other structured liquids are liquid laundry detergents.This characteristic helps to solve the settled problem of pigment, but still can keep the flowing property of thin fluids simultaneously, and this helps to reach the surface of good fraction of coverage as the product of liquid wash basin sanitising agent.Said composition also has good phase stability and hypochlorite stability.
Composition of the present invention comprises: (a) alkaline metal hypochlorite, preferred clorox, (b) wilkinite, (c) have the chain alkyl of a 10-16 carbon atom and the tertiary amino oxides of two low alkyl groups, (d) an alkali metal salt, preferred sodium-chlor, (e) pH stablizer, make pH 11 or higher, (f) basic metal C 10-C 16Alkyl sarcosine salt, (g) C 10-C 14Linear alkylbenzene sulfonate and (h) mineral dye, preferred ultramarine.Can realize above-described rheological property of making us wishing and phase stability by blending clay, tensio-active agent and ionogen.Particularly, tertiary amino oxides (c) is about 5 with the mol ratio of alkylbenzene sulfonate (g): about 11: 1 of 1-.Do not use pigment (h), can make and be similar to the useful composition that is unstained of the present invention.
The viscosity scope of said composition is the about 1000cps of about 200-.Preferable range is about 300-500cps.
The accompanying drawing summary
Fig. 1 and 2 is the figure of rheological property of expression the present invention's preferred embodiment.
Fig. 3 and 4 is some rheological property of the composition (Fig. 3) of expression according to the present invention and the figure that does not have analogous composition (Fig. 4) reduced property of clay.
Describe in detail
The present composition is stable, the single-phase of hypochlorite, and comparing with rarer composition is the thickness hypochlorite bleaching compositions that can stick to for more time on vertical or the inclined surface. Said composition is to stain and the foul effective reagent of removing and sterilize. High-caliber hypochlorite stability and the single solution phase characteristic of said composition make it have the acceptable storage life. Said composition also is included in the organic pigment in the suspension. In these colored compositions, colour stability during as pigment, is very favorable in ultramarine particularly.
Alkali metal among the alkali metal hypochlorite is preferably selected from: lithium, potassium or sodium. From cost and being easy to get property, clorox is preferred. The alkali metal hypochlorite can produce other accessory substance in preparation process, but can not have a negative impact to composition. Alkali metal hypochlorite's consumption is about 0.5wt%-10wt%, is preferably about 1.0wt%-5.0wt%, more preferably from about 1.5wt%-3.0wt%.
Bentonite is the colloidal silicate hydrate alum clay of finding in the North America. Its basic composition is imvite (Al2O 3.4SiO 2.H 2O), and usually contain magnesium, iron and calcium carbonate. Bentonite is preferred in the present invention's the composition, but the clay of other analog structures and/or character also can use. The consumption of bentonite in composition be at about 0.15wt%-1.5wt%, preferably about 0.25wt%-1.0wt %. The structural formula of tertiary amino oxides is:
Figure A9619618500091
Wherein, R1The alkyl that comprises about 10-16 carbon atom, R2And R3It is the low alkyl group that comprises 1-3 carbon atom. R1、R 2And R3Can be straight chain also can be side chain; R1Comprise odd number or even number of carbon atoms. Can use the amine oxide that mixes chain length, it can comprise main one or more chain lengths. Preferably, tertiary amino oxides is selected from: myristyl dimethyl amine oxide, dodecyl-dimethyl amine oxide and their mixture. What most preferably use is myristyl dimethyl amine oxide. The consumption of tertiary amino oxides is preferably about 0.5wt%-2.5wt %, more preferably from about 0.9wt%-1.8wt%, most preferably from about 1.0wt%-1.5wt%.
Alkali metal salt can be selected from many water-soluble alkali metal salts and composition thereof, and wherein alkali metal is preferably lithium, potassium or sodium, and anion is preferably halogen ion (such as chlorine, fluorine, bromine and iodide ion). Preferred alkali metal salt is to be selected from sodium chloride, lithium chloride, potassium chloride and their mixture. From cost and being easy to get property, alkali metal salt most preferably is sodium chloride, and can various amounts use, and avoids occurring salting out in the solution (this moment, surfactant became water insoluble) to reduce the degraded of hypochlorite, just to be limited to. When using sodium chloride, preferred use amount is about 0.25wt%-2.0wt%, more preferably from about 0.5wt%-1.5wt%.
Alkali metal hydroxide is the pH stabilizing agent that preferably is included in the composition, but also can use various pH stabilizing agents, as long as stability and the viscosity of composition is not had negative effect. Spendable other pH stabilizing agents for example comprise carbonate buffer agent. The alkali metal of preferred hydroxide can be lithium, potassium or sodium. Because cost and being easy to get property, NaOH and potassium hydroxide are particularly preferred pH stabilizing agents, and NaOH is most preferred. The alkali metal hydroxide amount in the composition of being included in be the pH that effectively regulates composition be at least 11, more preferably 12-13.5, most preferably be the amount of 12-13.
The basic metal alkyl sarcosine salt can be represented with following structural formula:
Figure A9619618500101
Wherein, R 4Be side chain or straight chain C 10-C 16Alkyl, M are alkali metal cation (as lithium, potassium or sodium).Sodium N-lauroyl sarcosinate is most preferred.The usage quantity of basic metal alkyl sarcosine salt is preferably about 0.10wt%-0.75wt%, more preferably from about 0.12wt%-0.60wt%, most preferably from about 0.15wt%-0.30wt%.
Basic metal C 10-C 14Linear alkylbenzene sulfonate preferably wherein basic metal be potassium, lithium or sodium.What most preferably use is Sodium dodecylbenzene sulfonate.The preferred usage quantity of sulfonate is about 0.08wt%-0.8wt%, and more preferably 0.1wt%-0.5wt% most preferably is 0.15wt%-0.40wt%.
In these colored compositions, preferred pigment is ultramarine, and it is an inorganic silicate.Oxidation is an inert though this material is to hypochlorite, and decomposition reaction that can the catalysis hypochlorite, and it is insoluble, need be suspended in the hypochlorite solutions.This suspension can not be only by the ultramarine particles dispersed is made in hypochlorite solutions, this is because the density of this pigment is 2.35, even and very thin particle also can sedimentation.The viscosity increasing system of using in the present invention's the composition provides excellent suspension effect for the ultramarine pigment particle.The usage quantity of ultramarine in the present invention's composition is about 0.01wt%-0.50wt%, is preferably about 0.05wt%.
The mol ratio of tertiary amino oxides and basic metal inorganic benzene sulfonate should be about 5: in about 11: 1 scope of 1-.Preferably, this mol ratio is 6: 1-10: 1, more preferably 7: 1-9: 1.
Said composition provides higher viscosity for alkaline metal hypochlorite's SYNTHETIC OPTICAL WHITNER, and commercial acceptable colored composition is provided simultaneously, and the colour stability of said composition is excellent.Though do not wish to link together, it is believed that main interaction is between the clay and amine oxide in composition with any special theory.In following preferred embodiment, the combination of clay, sodium-chlor and sodium hydroxide solution makes clay particle produce limit-face structural arrangement.Some amine oxides have reached the effect of rock steady structure by ion and cubic phase mutual effect.Sulfonate and sarcosinate surfactant combine with remaining amine oxide, the micella that forms organic structure or tackify.Further theory is, these micellas and caly structure interact, and has produced unique rheological characteristics of composition.
The invention provides commercially beneficial coloured thickening system, this system has thixotropy, is easy to especially distribute from automiser spray.Use the cleaning product of this thickening system to have sufficiently high static viscosity, inorganic pigment granules is stabilized in the suspension.
Reference example will be understood the present invention better, and these embodiment only are used for explanation, but not be used for restriction.
Embodiment 1
The watch face sanitising agent that preparation is blue; it has following component, and all percentage ratios all are weight percentage. component bentonites (Gelwhite H) 1.00% ultramarine 0.05% sodium chloride 1.00% NaOH 2.50% myristyl dimethyl amine oxide 5.60% clorox 2.50% neopelex 0.72% sodium N-lauroyl sarcosinate 1.00% spices 0.065% deionized water balance to 100%
Prepare this cleaning compositions by the following method: in main vessel (1), use homogenizer that Gelwhite H--polynite (Southern Clay Products) is dispersed in the water, by hydration fully, under vigorous stirring, add ultramarine then until clay.In another container (2), sodium-chlor and 25% aqueous sodium hydroxide solution are dissolved in the water.The content of container (2) adds in the container (1), and vigorous stirring.Add all the other components in the following order, and stir: Ammonyx MO, 30% tetradecyl dimethyl amine oxide solution, StepanCompany; Spices; 16.67% solution of sodium hypochlorite bleaching agent; Biosoft D-40,40% Sodium dodecylbenzene sulfonate solution, Stepan Company; With Hamposyl L-30,30% sodium N-lauroyl sarcosinate solution, W.R.Grace ﹠amp; Company.
Fig. 1 shows the rheology figure of this preferred embodiment.It summarizes shear-stress is the function of time when four kinds of shearing rates.When constant shearing condition, said composition is 1 and 10sec -1The time all be rheopecticity.At 50sec -1Shi Mingxian is thixotropic.Fig. 2 has caught at the first shearing rate 1sec -1The time stress when initial flow increase behavior.Test is carried out with RheometricsScientific RFSII rheometer, 50mm parallel plate, 0.9mm interval, 316SS mould, 25 ℃, 0.002-10gr-power reequilibrate.
There is not the analogous composition of clay and pigment component to show diverse rheological property.See Fig. 3 and 4.Checking G ' and G " in the coordinate diagram; wherein G ' is measuring of emphasizing of the elasticity of viscoelastic fluid; G " be measuring of the mechanical energy that dissipates between deformation phases of structural fluid, the characteristic and the attach structure fluid of composition with clay is similar, has tangible strain-dependent.Characteristic does not have tangible strain-dependent to the similar composition of the characteristic that mainly is viscous fluid.This difference shows the obvious interaction between composition medium clay soil component and the tensio-active agent.
Embodiment 2-5
According to the method for embodiment 1, prepare following composition:
Component Embodiment 2 % Embodiment 3 % Embodiment 4 % Embodiment 5 %
Polynite (Gelwhite H) 1.00 1.00 1.00 1.00
Ultramarine 0.05 0.05 0.05 0.05
Sodium-chlor - 1.00 - 1.00
Repone K - - 1.27 -
Sodium hydroxide (25% aqueous solution) 2.50 2.50 - 2.500
Potassium hydroxide - - 0.88 -
Tetradecyl dimethyl amine oxide compound (30%) 5.60 4.20 5.60 5.60
Dodecyl dimethyl amine oxide (30%) - 1.40 - -
Clorox 2.50 2.50 2.50 2.50
Sodium N-lauroyl sarcosinate (30%) 1.00 1.00 1.00 -
Tetradecyl sodium sarcosinate (30%) - - - 1.10
Sodium dodecylbenzene sulfonate (40%) 0.72 0.72 0.72 0.72
Spices 0.07 0.07 0.07 0.07
Deionized water To 100 To 100 To 100 To 100
Comparative Examples
Preparation comprises ultramarine pigment but does not have bentonitic cleaning compositions, compares with the pigment settling character of embodiment 1 composition.Use the method for embodiment 1 to prepare comparative composition.Two compositions are remained on 6 weeks of stationary state under 40 ℃.Following table shows the component of these two compositions and relevant rheological data.
Table
Component Embodiment
1 Comparative Examples
Wilkinite 1.00％ --
Ultramarine 0.05％ 0.025％
Sodium-chlor 1.00％ 1.00％
Sodium hydroxide 2.50％ 2.60％
Tetradecyl dimethyl amine oxide compound (30%) 5.60％ 6.20％
Clorox 2.50％ 2.50％
Sodium dodecylbenzene sulfonate (40%) 0.72％ 0.80％
Sodium N-lauroyl sarcosinate (30) 1.00％ 1.00％
Spices 0.065％ 0.075％
Deionized water To 100% To 100%
Viscosity 464 448
The pigment sedimentation 6 Zhou Houwu Sedimentation during the 3rd week
These data show, and are opposite with the excellent suspension characteristic of embodiment 1, in the Comparative Examples of the pigment that only comprises half amount, begin sedimentation in three weeks.

Claims (6)

1, the colored hypochlorite aqueous composition of a kind of heavy-gravity is that benchmark comprises with weight: (a) alkaline metal hypochlorite of 0.5%-10%; (b) wilkinite of 0.25%-1%; (c) the following formula tertiary amino oxides of 0.5%-2.5%
Figure A9619618500021
Wherein, R 1Be the alkyl that comprises 10-16 carbon atom, R 2And R 3It is respectively the alkyl that comprises 1-3 carbon atom; (d) an alkali metal salt of 0.25%-0.2%; (e) significant quantity is to make pH 11 or higher pH stablizer; (f) the following formula basic metal sarcosinate of 0.10%-0.75%:
Figure A9619618500022
Wherein, R 4It is straight chain C 10-C 16Alkyl, M are lithium, sodium or potassium; (g) the basic metal alkylbenzene sulfonate of 0.08-0.80%, wherein alkyl be straight chain and contain 10-14 carbon atom; (h) mineral dye of 0.01%-0.5% wherein, is 5 with (g) mol ratio (c): 1-11: 1.
2, hypochlorite compositions as claimed in claim 1, wherein (h) pigment is ultramarine.
3, hypochlorite compositions as claimed in claim 2, wherein (a) described alkaline metal hypochlorite is a clorox; (c) described amine oxide is dodecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide compound or their mixture; (d) described an alkali metal salt is a sodium-chlor; (e) described pH stablizer is a sodium hydroxide, presents in an amount at least sufficient to make pH at 12-13.5; (f) described sarcosinate sodium N-lauroyl sarcosinate; (g) described basic metal alkylbenzene sulfonate is a Sodium dodecylbenzene sulfonate.
4, hypochlorite compositions as claimed in claim 3, wherein (c) amine oxide is the dodecyl dimethyl amine oxide.
5, hypochlorite compositions as claimed in claim 4, it comprises (by weight) (a) clorox of 1%-5%; (b) wilkinite of 0.25%-1%; (c) the dodecyl dimethyl amine oxide of 0.9%-1.8%; (d) sodium-chlor of 0.5%-0.15%; (f) sodium N-lauroyl sarcosinate of 0.12%-0.60%; (g) Sodium dodecylbenzene sulfonate of 0.10-0.50%; (h) about 0.05% ultramarine pigment wherein, is 6 with (g) mol ratio (c): 1-10: 1.
6, hypochlorite compositions as claimed in claim 5, it comprises (by weight) (a) clorox of 1.5%-3.0%; (c) the dodecyl dimethyl amine oxide of 1.0%-1.5%; (f) sodium N-lauroyl sarcosinate of 0.15%-0.30%; (g) Sodium dodecylbenzene sulfonate of 0.15-0.40%; Wherein, (c) be 7: 1-9: 1 with (g) mol ratio.
CN96196185A 1995-08-10 1996-07-08 Pigmented rheopectic cleaning compositions with thioxotropic properties Expired - Fee Related CN1102649C (en)

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GB9516372.1 1995-08-10
GB9516372A GB2304113B (en) 1995-08-10 1995-08-10 Hard surface cleaner
US08/619,864 1996-03-18
US08/619,864 US5688435A (en) 1995-08-10 1996-03-18 Pigmented rheopectic cleaning compositions with thixotropic properties

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CN1102649C CN1102649C (en) 2003-03-05

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BR9609898A (en) 1999-05-25
AU692718B2 (en) 1998-06-11
CA2228674A1 (en) 1997-02-20
NZ313386A (en) 1998-07-28
CA2228674C (en) 2000-10-10
AU6543196A (en) 1997-03-05
MX9801081A (en) 1998-04-30
EP0859826A1 (en) 1998-08-26
WO1997006233A1 (en) 1997-02-20
EP0859826A4 (en) 1999-11-24
CN1102649C (en) 2003-03-05
IN189237B (en) 2003-01-11

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