CA2228674C - Pigmented rheopectic cleaning compositions with thixotropic properties - Google Patents
Pigmented rheopectic cleaning compositions with thixotropic properties Download PDFInfo
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- CA2228674C CA2228674C CA002228674A CA2228674A CA2228674C CA 2228674 C CA2228674 C CA 2228674C CA 002228674 A CA002228674 A CA 002228674A CA 2228674 A CA2228674 A CA 2228674A CA 2228674 C CA2228674 C CA 2228674C
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- hypochlorite
- sodium
- alkali metal
- weight
- oxide
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Biological Depolymerization Polymers (AREA)
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
W O 97/06233 1 PCT~US96/11409 PIGMENTED RHEOPECTIC CLEANING COMPOSITIONS
WITH THIXOTROPIC PROPERTIES
Field of the Invention This invention relates to thickened liquid bleach-cc.. ~ compositions useful for hard surface cle~ning, and particular to such compositions which include bleach-stable pigments.
Back~round of the Invention Thickened bleach compositions possess a number of advantages over unthickened bleach compositions. The more viscous, thickened solutions a&ere to vertical and inclined surfaces for a longer period of time as co~ aled or disinfectant activity of the thickened compositions is more effective on the int~nclefl areas.
To provide a thickened hypochlorite composition having an acceptable shelf-life, the rate of decomposition of alkali metal hypochlorite as well as the phase behaviour of the composition must be considered. As is known, alkali metalhypochlorite degradation may be illustrated by the following equation:
WITH THIXOTROPIC PROPERTIES
Field of the Invention This invention relates to thickened liquid bleach-cc.. ~ compositions useful for hard surface cle~ning, and particular to such compositions which include bleach-stable pigments.
Back~round of the Invention Thickened bleach compositions possess a number of advantages over unthickened bleach compositions. The more viscous, thickened solutions a&ere to vertical and inclined surfaces for a longer period of time as co~ aled or disinfectant activity of the thickened compositions is more effective on the int~nclefl areas.
To provide a thickened hypochlorite composition having an acceptable shelf-life, the rate of decomposition of alkali metal hypochlorite as well as the phase behaviour of the composition must be considered. As is known, alkali metalhypochlorite degradation may be illustrated by the following equation:
2 o NaOC 1 ~ NaC 1 + I/2 ~2 Many con~ lional thickening agents accelerate the degradation of the hypochlorite and thus are problematic for use in hypochlorite compositions. Also, ~ the inclusion of conventional thickening agents and surf~ct~nt~ is difficult because 2 5 the resulting hypochlorite composition has a tendency to separate into two or more phases, particularly at elevated temp-,ldLules. Many thickening agents are ~emselves unsta'ble in the presence of an alkali metal hypochlorite. Thus, SUBSTITUTF SHEEl ~ULE26~
W O 97/06233 2 PCT~US96/11409 achieving sufficient viscosity in hypochlorite compositions by conventional agents and additives in addition to providing a hypochlorite composition having acceptable stability is difficult.
It is also desirable, for commercial and aesthetic reasons, to provide 5 thickened bleach-cont~ining cleaner compositions which have distinctive coloration. The realm of bleach stable colourants is fairly small due to the tendency of organic dyes to degrade in the presence of strong oxidizers.
U.S. Patent No. 4,474,677 (Foxlee) suggests the use of certain halogenated copper phthalocyanine pigments for aqueous alkali metal hypochlorite l o compositions. While this class of pigments is considered to be bleach-stable, slow degradation of the pigment molecule releases copper which catalyzes the degradation of hypochlorite. U.S. PatentNo. 4,271,030 (Brierley) describes a suspension of ultramarine blue using calcium soap flocs. Use of calcium soap flocs is not desirable due to the high concentration required, 50% by volume of the 15 composition, or from a cleaning standpoint due to a tendency to precipitate onto hard surfaces. U.S. Patent No. 4,952,333 (Cramer) describes a bleaching and brightening composition using polymers to suspend ultramarine blue in an Pm~ ified polymer matrix. This composition however would not be an effective hard surface cleaner due to its low detergency. U.S. PatentNo. 4,917,814 20 (MacIntyre) describes the use of cobalt ~lllmin~te to colour thickened hypochlorite solutions. Cobalt pi~nentc were found to be superior to ultramarine blue for suspension properties. While this is not disputed, it should be pointed out that, under higher temperature conditions than employed in MacIntyre, surfactant thickened compositions will lose viscosity and allow se-liment~tion of the pigment.
25 Consumer products require stability when exposed to these higher te~ cl~luies during distribution and storage.
~lJBST~TUTE SHEET ~RULE 26~
- SummarY of the Invention This invention provides thickened hypochlorite compositions with enhanced rheological pr~c,lies which are capable of stably suspending inorganic pigments.The thickening system is a blend of surfactants and clay that is rheopectic at low 5 shear rates, which helps to stably suspend the pigment, but thixotropic at higher shear rates, which allows the product to dispense easily from a container to aid in the cleaning of hard surfaces. By definition, rheopexy and thixotropy are opposite flow properties. Having both properties present in a single fluid is quite advantageous.
Non-limiting examples of inorganic colourants that can be ~ltili7e(1, include ultramarine blue, cobalt alllmin~te blue, Lil~iulll dioxide and calcium carbonate.
This invention focuses on the use of ultramarine blue which is preferred due to its consumer appeal, low toxicity, and colour intensity col.l~aled to other pigments.
The composition behaves as a highly structured liquid and exhibits some unique and unexpected flow properties. This occurs despite the low solids content, less than 10%, of the formula as compared to other structured liquids, some of which are known in the category of liquid laundry d~l~ .genl~. This characteristic helps to solve the problem of pigment se-lim~nt~tion while still m~int~inin~ thin fluid flow properties which help to achieve good surface coverage for products 2 o such as liquid toilet bowl cleaners. The composition also has good phase-stability and hypochlorite-stability.
The compositions of this invention comprise:
(a) an alkali metal hypochlorite, preferably sodium hypochlorite, (b) bentonite clay, 2 5 (c) a tertiary amine oxide having one long-chain alkyl group of from 10 to 16 carbon atoms and two lower alkyl groups, (d) an alkali metal salt, preferably sodium chloride, SUB~ 111 IJTE SHEET (RULE 26) -(e) a pH stabilizer to provide a pH of l l or higher, an alkali metal Clo- Cl6 alkyl sarcosinate, (g) a Clo - Cl4 straight chain alkylbenzène sulphonate, and (h) an inorganic pigment, preferably ultramarine blue.
5 The desired rheological properties and phase stability described above are achieved through the careful blending of clay, surfactants and electrolytes. In particular, the molar ratio of the tertiary amine oxide (c) to the alkylbenzene sulphonate (g) should range from about 5: l to about l l: l . Useful non-pigmented compositionsanalogous to the compositions of this invention can be ~l~paled without the 10 pigment (h).
The viscosity of the composition can range from about 200 cps to about lO00 cps. The preferred range is from about 300 - S00 cps.
Brief Description of the Drawin~s Figures l and 2 are graphs showing the rheological properties of a preferred embodiment of this invention.
Figures 3 and 4 are graphs showing certain rheological properties of a for~ tion according to this insertion (Figure 3) and conl~al~ble properties of asimilar composition without the clay (Figure 4).
Detailed Disclosure The inventive composition is a hypochlorite stable, single phase, thickened hypochlorite bleach composition capable of adhering to vertical or inclined surfaces longer than thinner compositions. The composition is an effective agent2 5 for stain and soil removal as well as disinfection. The high level of hypochlorite stability and single solution phase behaviour of the composition enables the composition to have an acceptable shelf life. The compositions include also an ~UBSTITUT~ SHEE~ ~RULE 26) W O 97/06233 5 PCTrUS96/11409 organic pigment in suspension. In these pigmented compositions, the colour stability, particularly where the pigment is ultramarine blue, is uniquely advantageous.
Preferably the alkali metal of the alkali metal hypochlorite is selected from 5 lithillm, potassium or sodium. For purposes of cost and availability, sodium hypochlorite is currently preferred. The alkali metal hypochlorite may have other by-products of the m~nllf~r*lring process present without adversely affecting the composition. The amount of alkali metal hypochlorite employed is within the range of about O.S weight % to about 10 weight %, preferably from 1.0 weight %
o to 5.0 weight %, and more preferably from l.S weight % to 3.0 weight %.
Bentonite clay is a colloidal hydrated alllminllm silicate clay found in North America. It consists principally of montmorillonite (A12O3.4SiO2.H2O) and usually also contains some magnesium, iron and calcium carbonate. Bentonite clay is preferred for use in the compositions of this invention, but other clays of 15 similar structure and/or properties may be used. The amount of Bentonite clay in the composition should range from about 0.15 weight % to about l.S weight %, preferably from 0.25 weight % to 1.0 weight %.
The tertiary amine oxide is of the formula:
Rl_N~
wherein Rl is an alkyl group cont~ining from about 10 to about 16 carbon atoms and each of R2 and R3 is a lower alkyl group cont~ining from 1 to 3 carbon atoms.
~UBSTITUTE S!~ET (RULE 26) ~1, R2 and R3 may be a straight or branched chain; Rl may contain an odd or an even number of carbon atoms. Amine oxides of mixed chain length may be used, which may contain a predomin~nce of one or more chain lengths. Preferably, the tertiary amine oxide is selected from myristyldimethylamine oxide, 5 lauryldimethylamine oxide, and mixtures thereof. Most preferably employed is myristyldimethylamine oxide. The amount of the tertiary amine oxide employed is pLerclably in the range from about 0.5 weight % to about 2.5 weight %, more preferably from 0.9 weight % to 1.8 weight %, and most preferably from 1.0 weight % to 1.5 weight %.
The alkali metal salt may be selected from any number of water-soluble alkali metal salts and mixtures thereof, with the alkali metal preferably being lithium, potassium, or sodium, and the anion ion preferably being a halide (such as chloride, fluoride, bromide and iodide). More preferably the alkali metal salt is selected from the group consisting of sodium chloride, lithium chloride, potassium chloride, and mixtures thereof. For purposes of cost and availability, the alkali metal salt most preferred is sodium chloride and may be used in varying amounts to reduce hypochlorite degradation, limited only by the avoidance of a "salting out" of the solution (where the surfactants become insoluble in water). When sodium chloride is used, the preferred amount is in the range of about 0.25 weight 2 0 % to about 2.0 weight %, preferably from 0.5 weight % to 1.5 weight %.
An alkali metal hydroxide is the plefe,led pH stabilizer included in the composition, although any pH stabilizer may be employed as long as the stabilityand viscosity of the composition are not adversely affected. Other pH stabilizers which may be used, for example, include carbonate buffers. The alkali metal of 2 5 the preferred hydroxide may be lithium, potassium, or sodium. Sodium hydroxide and potassium hydroxide are particularly useful pH stabilizers due to cost and availability, with sodium hydroxide most preferred. The alkali metal hydroxide is SUBSTITUTE SHEET (RULE 26) W O 97/0~233 7 PCT~US96/11409 included in the composition in an effective amount to adjust the composition to a pH level of at least about 11, more preferably from 12 to 13.5, and most preferably within the range from 12 to 13.
The alkali metal alkyl sarcosinate may be represented by the formula:
R4 - C - N - CH2COO- M+
ll 0 wherein R4 is a branched or straight chain ~ 1 o-C 16 alkyl group and M is an alkali metal cation (such as lithium, potassium or sodium). Sodium lauroyl sarcosinate is most ~rere~.~ d. The amount of alkali metal alkyl sarcosinate that may be used preferably ranges from about 0.10 weight % to about 0 75 weight %, more preferably 0.12 weight % to 0.60 weight %, and most preferably from 0.15 weight % to 0.30 weight %.
The aL~ali metal Clo to C14 straight chain alkylbenzene sulphonate is preferably defined wherein the alkali metal is pot~eil-m, lithium, or sodium. Most preferably employed is sodium dodecylbenzene sulphonate. Preferably the àmount of sulphonate used is within the range of from about 0.08 weight % to about 0.8 2 o weight %, more preferably from 0.1 weight % to 0.5 weight %, and most preferably from 0.15 weight % to 0.4 weight %.
In these pi~nen~ed compositions, the plerc.l~,d pigment is ultramarine blue which is an inorganic silicate. Although this material is inert to hypochlorite oxidation and does not catalyze decomposition of hypochlorite, it is insoluble and 2 5 requires suspension in the hypochlorite solution. Such suspension cannot be achieved merely by dispensing particles of ultramarine blue in hypochlorite solution, because the pigment has a density of 2.35 and settles out even when it is of very fine particle size. The thickening system employed in the composition ofthis invention provides excellent suspension for ultramarine blue pigment particles.
SIJBSTITUTE SHEET ~RULE 26) W O 97/06233 8 PCT~US96/11409 The amount of ultramarine blue in the composition of this invention ranges from about 0.01 weight % to about 0.50 weight %, preferably about 0.05 weight %.
The molar ratio of the tertiary amine oxide to alkali metal alkylbenzene sulphonate should fall within the range of from about 5 :1 to about 1 1:1.
5 Preferably, the molar ratio is from 6:1 to 10:1, and more preferably from 7:1 to 9:1.
The composition offers improved viscosity for alkali metal hypochlorite bleaches while at the same time providing a commercially acceptable pigmented composition with excellent colour stability. Although not wishing to be bound to10 any particular theory, it is believed that the primary interaction is between the clay and the amine oxide components of the formula. In the preferred embo-liment of the example set forth below, the combination of the clay, sodium chloride, and the sodium hydroxide in solution causes the clay platelets to align in an edge-to-face structure. Some of the amine oxide acts to stabilize the structure through both 15 ionic and steric interaction. Sulphonate and sarcosinate surf~t~nt~ combine with the rem~inin~ amine oxide to forrn organic structures or micelles which boost viscosity. It is further theorized that these micelles interact with the clay structure to develop the unique rheology of the composition.
This invention provides a commercially advantageous coloured thickening 2 0 system which exhibits thixotropic properties for easy dispensing, particularly from a spray container. Cleaning products employing this thickening system have a sufficiently high level of quiescent viscosity to keep the inorganic pigment particles in suspension.
The invention will be better understood by reference to the following 2 5 examples which are included for the purpose of illustration, and are not be be construed as limit~tions.
~UBSTITUTE SHEET (RULE 26) W O 97/06233 9 PCT~US96/11409 Example l A blue-pigmented hand surface cleaner was prepared which had the following ingredients, all percentages being by weight.
In~redient bentonite clay (Gelwhite H) 1.00%
ultramarine blue 0.05%
sodium chloride 1.00%
sodium hydroxide 2.50%
myristyldimethylamine oxide 5.60%
sodium hypochlorite 2.50%
sodium dodecylbenzene sulphonate 0.72%
sodium lauroyl sarcosinate 1.00%
fragrance 0.065%
deionized water q.s. to 100%
The cleaner composition was p~ ed by dispensing in the main vessel ( l) Gelwhite H, a montmorillomite clay (Southern Clay Products) in water, using a homogenizer until the clay is fully hydrated, and adding the Ultramarine blue with further agitation. In a separate vessel (2), sodium chloride and a 25% solution of 2 o sodium hydroxide were dissolved in water. The contents of vessel (2) were added to vessel (l) with high agitation. The rem~ining ingredients were added, with agitation, in the following order: Ammonyx MO, a 30% solution of myristyldimethylamine oxide, Stepan Company; fragrance; a 16.67% solution of sodium hypochlorite bleach; Biosoft D-40, a 40% solution of sodium 25 dodecylbenzene sulphonate, Stepan Company; and Hamposyl L-30, a 30% solution of sodium lauroyl sarcosinate, W.R. Grace & Co~ y.
~UBSTITUTE SHEET ~RlJLE 26) Figure 1 shows the rheology profile of this preferred embodiment. It snmm~rizes the shear stress as a function of time at four shear rates. The formula appears to be rheopectic at both 1 and 10 sec-l, under conditions of constant shear.
The thixotropic character is evident at 50 sec~l. Figure 2 captures the stress growth 5 behaviour at the inception of flow at the first shear rate, 1 sec~ 1. Testing was conducted with the Rheometrics Scientific RFSII rheometer, 50 mm parallel plate,0.9 mm spacing, 316SS tooling, 25C, 0.002 - 10 gr-cm force rebalance.
An analogous formula without the clay and pigment components exhibits dramatically different rheological properties. See Figures 3 and 4. In the 10 e~min~tion of plots of G', a measure of the elastic strength of a viscoelastic fluid, and G' ', a measure of the mechanical energy dissipated during the deformation of structured fluid, the formula with clay behaves as a highly structured fluid with significant strain dependence. The analogous formula behaves as a predominzmtly viscous fluid with no significant strain dependence. This difference indicates a15 significant interaction between the clay component and the surfactants present in the forrn~ tion.
Examples 2-5 Following the procedure of Example 1, the following additional compositions were prepared:
SUBSTITUTE SHEET (RULE 26) W O 97/06233 11 PCT~US96/11409 v~ 8 -- o ~ o o o o o ~, ~
~1 ~. ~. ? ~ ~", ~ . V,, _ _ o o ~ -- ~ O O
o .~ o ~ 1-- oo o o o ~ ~ --~1 ~ ~ ' ~ ' ~ ~ "'' -- ~ ~ U~
o o . ~ ~ o o o o o ~ t-- --~1 ~ ~ ~' ~ ' ~ ~ ~ a~
C'l o -- o ~ o o o o ~ ~
~1 o. o., , u~, ~, v~ o., _ o. o _ o ~ V~ ~ _ o o X r r~
O
X .
~ ~ O ~ ~
a ~? a a O ~ ~ ~ ~ o ~ O
SUBSTITUTE SHE~T (RUI E 26) W O 97/06233 ~2 PCT~US96/11409 Comparative Example A cleaning composition containing ultramarine blue pigment, but without bentonite clay was pr~aled, and the pigrnent-settling characteristics were co~ ~ed with the composition of Example 1. The comparative composition was 5 ~l~al~d using the method of Example 1. The two compositions were m~int~ined in a quiescent state for a period of six weeks at 40~C. The following table shows the ingredients of the compositions and the relevant rheological data.
TABLE
(~omparative In~redient Example 1 Example bentonite clay 1.00% --ultramarine blue 0.05% 0.025%
sodium chloride 1.00% 1.()0%
sodium hydroxide 2.50 % 2.60 %
myristyldimethylamine oxide (30%) 5.6()% 6.20 %
sodium hypochlorite 2.50 % 2.50 %
sodium dodecylbenzene sulphonate (40 % ) 0./2 % 0.~0 %
sodium lauroylsarcosinate (30%) 1.00% 1.0()%
~agrance 0.~65 % 0.0 /5%
deionized water q.s. to 1(~0% q.s. to 100%
viscosity 464 448 pigment settling none a~ter 6 settled during 3l~1 weeks week 10 These data show that, in contrast to the excellent suspension characteristics of Example 1, in the Comparative Example, which contains only half the amount of pigment, settles out within three weeks.
SIJBSTITUTE SHEET (RULE 26) _
W O 97/06233 2 PCT~US96/11409 achieving sufficient viscosity in hypochlorite compositions by conventional agents and additives in addition to providing a hypochlorite composition having acceptable stability is difficult.
It is also desirable, for commercial and aesthetic reasons, to provide 5 thickened bleach-cont~ining cleaner compositions which have distinctive coloration. The realm of bleach stable colourants is fairly small due to the tendency of organic dyes to degrade in the presence of strong oxidizers.
U.S. Patent No. 4,474,677 (Foxlee) suggests the use of certain halogenated copper phthalocyanine pigments for aqueous alkali metal hypochlorite l o compositions. While this class of pigments is considered to be bleach-stable, slow degradation of the pigment molecule releases copper which catalyzes the degradation of hypochlorite. U.S. PatentNo. 4,271,030 (Brierley) describes a suspension of ultramarine blue using calcium soap flocs. Use of calcium soap flocs is not desirable due to the high concentration required, 50% by volume of the 15 composition, or from a cleaning standpoint due to a tendency to precipitate onto hard surfaces. U.S. Patent No. 4,952,333 (Cramer) describes a bleaching and brightening composition using polymers to suspend ultramarine blue in an Pm~ ified polymer matrix. This composition however would not be an effective hard surface cleaner due to its low detergency. U.S. PatentNo. 4,917,814 20 (MacIntyre) describes the use of cobalt ~lllmin~te to colour thickened hypochlorite solutions. Cobalt pi~nentc were found to be superior to ultramarine blue for suspension properties. While this is not disputed, it should be pointed out that, under higher temperature conditions than employed in MacIntyre, surfactant thickened compositions will lose viscosity and allow se-liment~tion of the pigment.
25 Consumer products require stability when exposed to these higher te~ cl~luies during distribution and storage.
~lJBST~TUTE SHEET ~RULE 26~
- SummarY of the Invention This invention provides thickened hypochlorite compositions with enhanced rheological pr~c,lies which are capable of stably suspending inorganic pigments.The thickening system is a blend of surfactants and clay that is rheopectic at low 5 shear rates, which helps to stably suspend the pigment, but thixotropic at higher shear rates, which allows the product to dispense easily from a container to aid in the cleaning of hard surfaces. By definition, rheopexy and thixotropy are opposite flow properties. Having both properties present in a single fluid is quite advantageous.
Non-limiting examples of inorganic colourants that can be ~ltili7e(1, include ultramarine blue, cobalt alllmin~te blue, Lil~iulll dioxide and calcium carbonate.
This invention focuses on the use of ultramarine blue which is preferred due to its consumer appeal, low toxicity, and colour intensity col.l~aled to other pigments.
The composition behaves as a highly structured liquid and exhibits some unique and unexpected flow properties. This occurs despite the low solids content, less than 10%, of the formula as compared to other structured liquids, some of which are known in the category of liquid laundry d~l~ .genl~. This characteristic helps to solve the problem of pigment se-lim~nt~tion while still m~int~inin~ thin fluid flow properties which help to achieve good surface coverage for products 2 o such as liquid toilet bowl cleaners. The composition also has good phase-stability and hypochlorite-stability.
The compositions of this invention comprise:
(a) an alkali metal hypochlorite, preferably sodium hypochlorite, (b) bentonite clay, 2 5 (c) a tertiary amine oxide having one long-chain alkyl group of from 10 to 16 carbon atoms and two lower alkyl groups, (d) an alkali metal salt, preferably sodium chloride, SUB~ 111 IJTE SHEET (RULE 26) -(e) a pH stabilizer to provide a pH of l l or higher, an alkali metal Clo- Cl6 alkyl sarcosinate, (g) a Clo - Cl4 straight chain alkylbenzène sulphonate, and (h) an inorganic pigment, preferably ultramarine blue.
5 The desired rheological properties and phase stability described above are achieved through the careful blending of clay, surfactants and electrolytes. In particular, the molar ratio of the tertiary amine oxide (c) to the alkylbenzene sulphonate (g) should range from about 5: l to about l l: l . Useful non-pigmented compositionsanalogous to the compositions of this invention can be ~l~paled without the 10 pigment (h).
The viscosity of the composition can range from about 200 cps to about lO00 cps. The preferred range is from about 300 - S00 cps.
Brief Description of the Drawin~s Figures l and 2 are graphs showing the rheological properties of a preferred embodiment of this invention.
Figures 3 and 4 are graphs showing certain rheological properties of a for~ tion according to this insertion (Figure 3) and conl~al~ble properties of asimilar composition without the clay (Figure 4).
Detailed Disclosure The inventive composition is a hypochlorite stable, single phase, thickened hypochlorite bleach composition capable of adhering to vertical or inclined surfaces longer than thinner compositions. The composition is an effective agent2 5 for stain and soil removal as well as disinfection. The high level of hypochlorite stability and single solution phase behaviour of the composition enables the composition to have an acceptable shelf life. The compositions include also an ~UBSTITUT~ SHEE~ ~RULE 26) W O 97/06233 5 PCTrUS96/11409 organic pigment in suspension. In these pigmented compositions, the colour stability, particularly where the pigment is ultramarine blue, is uniquely advantageous.
Preferably the alkali metal of the alkali metal hypochlorite is selected from 5 lithillm, potassium or sodium. For purposes of cost and availability, sodium hypochlorite is currently preferred. The alkali metal hypochlorite may have other by-products of the m~nllf~r*lring process present without adversely affecting the composition. The amount of alkali metal hypochlorite employed is within the range of about O.S weight % to about 10 weight %, preferably from 1.0 weight %
o to 5.0 weight %, and more preferably from l.S weight % to 3.0 weight %.
Bentonite clay is a colloidal hydrated alllminllm silicate clay found in North America. It consists principally of montmorillonite (A12O3.4SiO2.H2O) and usually also contains some magnesium, iron and calcium carbonate. Bentonite clay is preferred for use in the compositions of this invention, but other clays of 15 similar structure and/or properties may be used. The amount of Bentonite clay in the composition should range from about 0.15 weight % to about l.S weight %, preferably from 0.25 weight % to 1.0 weight %.
The tertiary amine oxide is of the formula:
Rl_N~
wherein Rl is an alkyl group cont~ining from about 10 to about 16 carbon atoms and each of R2 and R3 is a lower alkyl group cont~ining from 1 to 3 carbon atoms.
~UBSTITUTE S!~ET (RULE 26) ~1, R2 and R3 may be a straight or branched chain; Rl may contain an odd or an even number of carbon atoms. Amine oxides of mixed chain length may be used, which may contain a predomin~nce of one or more chain lengths. Preferably, the tertiary amine oxide is selected from myristyldimethylamine oxide, 5 lauryldimethylamine oxide, and mixtures thereof. Most preferably employed is myristyldimethylamine oxide. The amount of the tertiary amine oxide employed is pLerclably in the range from about 0.5 weight % to about 2.5 weight %, more preferably from 0.9 weight % to 1.8 weight %, and most preferably from 1.0 weight % to 1.5 weight %.
The alkali metal salt may be selected from any number of water-soluble alkali metal salts and mixtures thereof, with the alkali metal preferably being lithium, potassium, or sodium, and the anion ion preferably being a halide (such as chloride, fluoride, bromide and iodide). More preferably the alkali metal salt is selected from the group consisting of sodium chloride, lithium chloride, potassium chloride, and mixtures thereof. For purposes of cost and availability, the alkali metal salt most preferred is sodium chloride and may be used in varying amounts to reduce hypochlorite degradation, limited only by the avoidance of a "salting out" of the solution (where the surfactants become insoluble in water). When sodium chloride is used, the preferred amount is in the range of about 0.25 weight 2 0 % to about 2.0 weight %, preferably from 0.5 weight % to 1.5 weight %.
An alkali metal hydroxide is the plefe,led pH stabilizer included in the composition, although any pH stabilizer may be employed as long as the stabilityand viscosity of the composition are not adversely affected. Other pH stabilizers which may be used, for example, include carbonate buffers. The alkali metal of 2 5 the preferred hydroxide may be lithium, potassium, or sodium. Sodium hydroxide and potassium hydroxide are particularly useful pH stabilizers due to cost and availability, with sodium hydroxide most preferred. The alkali metal hydroxide is SUBSTITUTE SHEET (RULE 26) W O 97/0~233 7 PCT~US96/11409 included in the composition in an effective amount to adjust the composition to a pH level of at least about 11, more preferably from 12 to 13.5, and most preferably within the range from 12 to 13.
The alkali metal alkyl sarcosinate may be represented by the formula:
R4 - C - N - CH2COO- M+
ll 0 wherein R4 is a branched or straight chain ~ 1 o-C 16 alkyl group and M is an alkali metal cation (such as lithium, potassium or sodium). Sodium lauroyl sarcosinate is most ~rere~.~ d. The amount of alkali metal alkyl sarcosinate that may be used preferably ranges from about 0.10 weight % to about 0 75 weight %, more preferably 0.12 weight % to 0.60 weight %, and most preferably from 0.15 weight % to 0.30 weight %.
The aL~ali metal Clo to C14 straight chain alkylbenzene sulphonate is preferably defined wherein the alkali metal is pot~eil-m, lithium, or sodium. Most preferably employed is sodium dodecylbenzene sulphonate. Preferably the àmount of sulphonate used is within the range of from about 0.08 weight % to about 0.8 2 o weight %, more preferably from 0.1 weight % to 0.5 weight %, and most preferably from 0.15 weight % to 0.4 weight %.
In these pi~nen~ed compositions, the plerc.l~,d pigment is ultramarine blue which is an inorganic silicate. Although this material is inert to hypochlorite oxidation and does not catalyze decomposition of hypochlorite, it is insoluble and 2 5 requires suspension in the hypochlorite solution. Such suspension cannot be achieved merely by dispensing particles of ultramarine blue in hypochlorite solution, because the pigment has a density of 2.35 and settles out even when it is of very fine particle size. The thickening system employed in the composition ofthis invention provides excellent suspension for ultramarine blue pigment particles.
SIJBSTITUTE SHEET ~RULE 26) W O 97/06233 8 PCT~US96/11409 The amount of ultramarine blue in the composition of this invention ranges from about 0.01 weight % to about 0.50 weight %, preferably about 0.05 weight %.
The molar ratio of the tertiary amine oxide to alkali metal alkylbenzene sulphonate should fall within the range of from about 5 :1 to about 1 1:1.
5 Preferably, the molar ratio is from 6:1 to 10:1, and more preferably from 7:1 to 9:1.
The composition offers improved viscosity for alkali metal hypochlorite bleaches while at the same time providing a commercially acceptable pigmented composition with excellent colour stability. Although not wishing to be bound to10 any particular theory, it is believed that the primary interaction is between the clay and the amine oxide components of the formula. In the preferred embo-liment of the example set forth below, the combination of the clay, sodium chloride, and the sodium hydroxide in solution causes the clay platelets to align in an edge-to-face structure. Some of the amine oxide acts to stabilize the structure through both 15 ionic and steric interaction. Sulphonate and sarcosinate surf~t~nt~ combine with the rem~inin~ amine oxide to forrn organic structures or micelles which boost viscosity. It is further theorized that these micelles interact with the clay structure to develop the unique rheology of the composition.
This invention provides a commercially advantageous coloured thickening 2 0 system which exhibits thixotropic properties for easy dispensing, particularly from a spray container. Cleaning products employing this thickening system have a sufficiently high level of quiescent viscosity to keep the inorganic pigment particles in suspension.
The invention will be better understood by reference to the following 2 5 examples which are included for the purpose of illustration, and are not be be construed as limit~tions.
~UBSTITUTE SHEET (RULE 26) W O 97/06233 9 PCT~US96/11409 Example l A blue-pigmented hand surface cleaner was prepared which had the following ingredients, all percentages being by weight.
In~redient bentonite clay (Gelwhite H) 1.00%
ultramarine blue 0.05%
sodium chloride 1.00%
sodium hydroxide 2.50%
myristyldimethylamine oxide 5.60%
sodium hypochlorite 2.50%
sodium dodecylbenzene sulphonate 0.72%
sodium lauroyl sarcosinate 1.00%
fragrance 0.065%
deionized water q.s. to 100%
The cleaner composition was p~ ed by dispensing in the main vessel ( l) Gelwhite H, a montmorillomite clay (Southern Clay Products) in water, using a homogenizer until the clay is fully hydrated, and adding the Ultramarine blue with further agitation. In a separate vessel (2), sodium chloride and a 25% solution of 2 o sodium hydroxide were dissolved in water. The contents of vessel (2) were added to vessel (l) with high agitation. The rem~ining ingredients were added, with agitation, in the following order: Ammonyx MO, a 30% solution of myristyldimethylamine oxide, Stepan Company; fragrance; a 16.67% solution of sodium hypochlorite bleach; Biosoft D-40, a 40% solution of sodium 25 dodecylbenzene sulphonate, Stepan Company; and Hamposyl L-30, a 30% solution of sodium lauroyl sarcosinate, W.R. Grace & Co~ y.
~UBSTITUTE SHEET ~RlJLE 26) Figure 1 shows the rheology profile of this preferred embodiment. It snmm~rizes the shear stress as a function of time at four shear rates. The formula appears to be rheopectic at both 1 and 10 sec-l, under conditions of constant shear.
The thixotropic character is evident at 50 sec~l. Figure 2 captures the stress growth 5 behaviour at the inception of flow at the first shear rate, 1 sec~ 1. Testing was conducted with the Rheometrics Scientific RFSII rheometer, 50 mm parallel plate,0.9 mm spacing, 316SS tooling, 25C, 0.002 - 10 gr-cm force rebalance.
An analogous formula without the clay and pigment components exhibits dramatically different rheological properties. See Figures 3 and 4. In the 10 e~min~tion of plots of G', a measure of the elastic strength of a viscoelastic fluid, and G' ', a measure of the mechanical energy dissipated during the deformation of structured fluid, the formula with clay behaves as a highly structured fluid with significant strain dependence. The analogous formula behaves as a predominzmtly viscous fluid with no significant strain dependence. This difference indicates a15 significant interaction between the clay component and the surfactants present in the forrn~ tion.
Examples 2-5 Following the procedure of Example 1, the following additional compositions were prepared:
SUBSTITUTE SHEET (RULE 26) W O 97/06233 11 PCT~US96/11409 v~ 8 -- o ~ o o o o o ~, ~
~1 ~. ~. ? ~ ~", ~ . V,, _ _ o o ~ -- ~ O O
o .~ o ~ 1-- oo o o o ~ ~ --~1 ~ ~ ' ~ ' ~ ~ "'' -- ~ ~ U~
o o . ~ ~ o o o o o ~ t-- --~1 ~ ~ ~' ~ ' ~ ~ ~ a~
C'l o -- o ~ o o o o ~ ~
~1 o. o., , u~, ~, v~ o., _ o. o _ o ~ V~ ~ _ o o X r r~
O
X .
~ ~ O ~ ~
a ~? a a O ~ ~ ~ ~ o ~ O
SUBSTITUTE SHE~T (RUI E 26) W O 97/06233 ~2 PCT~US96/11409 Comparative Example A cleaning composition containing ultramarine blue pigment, but without bentonite clay was pr~aled, and the pigrnent-settling characteristics were co~ ~ed with the composition of Example 1. The comparative composition was 5 ~l~al~d using the method of Example 1. The two compositions were m~int~ined in a quiescent state for a period of six weeks at 40~C. The following table shows the ingredients of the compositions and the relevant rheological data.
TABLE
(~omparative In~redient Example 1 Example bentonite clay 1.00% --ultramarine blue 0.05% 0.025%
sodium chloride 1.00% 1.()0%
sodium hydroxide 2.50 % 2.60 %
myristyldimethylamine oxide (30%) 5.6()% 6.20 %
sodium hypochlorite 2.50 % 2.50 %
sodium dodecylbenzene sulphonate (40 % ) 0./2 % 0.~0 %
sodium lauroylsarcosinate (30%) 1.00% 1.0()%
~agrance 0.~65 % 0.0 /5%
deionized water q.s. to 1(~0% q.s. to 100%
viscosity 464 448 pigment settling none a~ter 6 settled during 3l~1 weeks week 10 These data show that, in contrast to the excellent suspension characteristics of Example 1, in the Comparative Example, which contains only half the amount of pigment, settles out within three weeks.
SIJBSTITUTE SHEET (RULE 26) _
Claims (6)
1. A thickened pigmented aqueous hypochlorite composition comprising, on a weight basis:
(a) from 0.5% to 10% of an alkali metal hypochlorite;
(b) from 0.25% to 1% of bentonite clay;
(c) from 0.5% to 2.5% of a tertiary amine oxide of the formula wherein R1 is an alkyl of from 10 to 16 carbon atoms, and each of R2 and R3 is alkyl of from 1 to 3 carbon atoms;
(d) from 0.25% to 2.0% of an alkali metal salt, (e) a pH stabilizer in sufficient amount to provide a pH of 11 or higher;
(f) from 0.10% to 0.75% of an alkali metal sarcosinate of the formula wherein R4 is a straight chain alkyl of from 10 to 16 carbon atoms and M is lithium, sodium or potassium;
(g) from 0.08 to 0.80% of an alkali metal alkylbenzene sulphonate in which the alkyl group is straight chained and has from 10 to 14 carbon atoms; and (h) from 0.01% to 0.5% of an inorganic pigment wherein the molar ratio of (c) to (g) ranges from 5:1 to 11:1.
(a) from 0.5% to 10% of an alkali metal hypochlorite;
(b) from 0.25% to 1% of bentonite clay;
(c) from 0.5% to 2.5% of a tertiary amine oxide of the formula wherein R1 is an alkyl of from 10 to 16 carbon atoms, and each of R2 and R3 is alkyl of from 1 to 3 carbon atoms;
(d) from 0.25% to 2.0% of an alkali metal salt, (e) a pH stabilizer in sufficient amount to provide a pH of 11 or higher;
(f) from 0.10% to 0.75% of an alkali metal sarcosinate of the formula wherein R4 is a straight chain alkyl of from 10 to 16 carbon atoms and M is lithium, sodium or potassium;
(g) from 0.08 to 0.80% of an alkali metal alkylbenzene sulphonate in which the alkyl group is straight chained and has from 10 to 14 carbon atoms; and (h) from 0.01% to 0.5% of an inorganic pigment wherein the molar ratio of (c) to (g) ranges from 5:1 to 11:1.
2. A hypochlorite composition according to claim 1 in which (h) the pigment is ultramarine blue.
3. A hypochlorite composition according to claim 2 in which:
(a) the alkali metal hypochlorite is sodium hypochlorite, (c) the amine oxide is lauryldimethylamine oxide, myristyldimethylamine oxide or mixtures thereof, (d) the alkali metal salt is sodium chloride, (e) the pH stabilizer is sodium hydroxide in sufficient amount to provide a pH of from 12 to 13.5, (f) the sarcosinate is sodium lauroyl sarcosinate, (g) the alkali metal alkylbenzene sulphonate is sodium dodecylbenzene sulphonate.
(a) the alkali metal hypochlorite is sodium hypochlorite, (c) the amine oxide is lauryldimethylamine oxide, myristyldimethylamine oxide or mixtures thereof, (d) the alkali metal salt is sodium chloride, (e) the pH stabilizer is sodium hydroxide in sufficient amount to provide a pH of from 12 to 13.5, (f) the sarcosinate is sodium lauroyl sarcosinate, (g) the alkali metal alkylbenzene sulphonate is sodium dodecylbenzene sulphonate.
4. A hypochlorite composition according to claim 3 in which (c) the amine oxide is lauryldimethylamine oxide.
5. A hypochlorite composition according to claim 4 which comprises, by weight (a) from 1% to 5% sodium hypochlorite, (b) from 0.25% to 1% bentonite clay, (c) from 0.9% to 1.8% lauryldimethylamine oxide, (d) from 0.5% to 1.5% sodium chloride, (f) from 0.12% to 0.60% sodium lauroyl sarcosinate, (g) from 0.10% to 0.50% sodium dodecylbenzene sulphonate, and (h) about 0.05% ultramarine blue pigment, wherein the molar ratio of (c) to (g) is from 6:1 to 10:1.
6. A hypochlorite composition according to claim 5 which comprises, by weight (a) from 1.5% to 3.0% sodium hypochlorite, (c) from 1.0% to 1.5% lauryldimethylamine oxide, (f) from 0.15% to 0.30% sodium lauroyl sarcosinate, and (g) from 0.15% to 0.40% sodium dodecylbenzene sulphonate, wherein the molar ratio of (c) to (g) ranges from 7:1 to 9:1.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9516372A GB2304113B (en) | 1995-08-10 | 1995-08-10 | Hard surface cleaner |
| GB9516372.1 | 1995-08-10 | ||
| US08/619,864 US5688435A (en) | 1995-08-10 | 1996-03-18 | Pigmented rheopectic cleaning compositions with thixotropic properties |
| US08/619,864 | 1996-03-18 | ||
| PCT/US1996/011409 WO1997006233A1 (en) | 1995-08-10 | 1996-07-08 | Pigmented rheopectic cleaning compositions with thixotropic properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2228674A1 CA2228674A1 (en) | 1997-02-20 |
| CA2228674C true CA2228674C (en) | 2000-10-10 |
Family
ID=26307551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002228674A Expired - Fee Related CA2228674C (en) | 1995-08-10 | 1996-07-08 | Pigmented rheopectic cleaning compositions with thixotropic properties |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0859826A4 (en) |
| CN (1) | CN1102649C (en) |
| AU (1) | AU692718B2 (en) |
| BR (1) | BR9609898A (en) |
| CA (1) | CA2228674C (en) |
| IN (1) | IN189237B (en) |
| MX (1) | MX9801081A (en) |
| NZ (1) | NZ313386A (en) |
| WO (1) | WO1997006233A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19722809A1 (en) * | 1997-05-30 | 1998-12-03 | Henkel Kgaa | cleaning supplies |
| GB9727517D0 (en) * | 1997-12-31 | 1998-02-25 | Jeyes Group Plc | Liquid bleach composition |
| DE19821695A1 (en) * | 1998-05-14 | 1999-11-25 | Henkel Kgaa | Stable coloring of solid or liquid machine dishwashing agents |
| AU3888500A (en) * | 1999-03-17 | 2000-10-04 | R.T. Vanderbilt Company, Inc | Stabilizer for bleach-containing cleaners |
| DE60217358T2 (en) * | 2002-10-29 | 2007-05-16 | Unilever N.V. | Thickened liquid bleaching compositions |
| US20040254085A1 (en) * | 2003-05-19 | 2004-12-16 | Johnsondiversey, Inc. | [high caustic contact cleaner] |
| DE102005058642B3 (en) * | 2005-12-07 | 2007-07-26 | Henkel Kgaa | Increasing the stability of liquid hypochlorite-containing detergents and cleaners |
| DE102005062008B3 (en) | 2005-12-22 | 2007-08-30 | Henkel Kgaa | Odor reduction of hypochlorite-containing agents |
| DE102005063177A1 (en) | 2005-12-30 | 2007-07-05 | Henkel Kgaa | Use of diethylene-penta-methylene phosphonic acid for the stabilization of optical brightener in aqueous liquid detergent containing alkali hypochlorite |
| DE102006003336A1 (en) * | 2006-01-23 | 2007-07-26 | Henkel Kgaa | Sprayable all-purpose cleaner |
| EP1911832A1 (en) * | 2006-10-13 | 2008-04-16 | Unilever N.V. | Bleaching composition |
| WO2009100227A1 (en) * | 2008-02-05 | 2009-08-13 | Amcol International Corporation | Drip resistant cleaning compositions |
| WO2018223368A1 (en) * | 2017-06-08 | 2018-12-13 | The Procter & Gamble Company | Non-homogeneous compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2849225A1 (en) * | 1977-11-18 | 1979-05-23 | Unilever Nv | POURABLE, LIQUID BLEACHING AGENTS |
| US4552680A (en) * | 1983-11-04 | 1985-11-12 | The Procter & Gamble Company | Hypochlorite bleach containing surfactant and organic antifoamant |
| US4623476A (en) * | 1984-03-30 | 1986-11-18 | The Procter & Gamble Company | Stable suspension of pigments in aqueous hypochlorite bleach compositions |
| US4714562A (en) * | 1987-03-06 | 1987-12-22 | The Procter & Gamble Company | Automatic dishwasher detergent composition |
| US4789495A (en) * | 1987-05-18 | 1988-12-06 | The Drackett Company | Hypochlorite compositions containing a tertiary alcohol |
| US5089162A (en) * | 1989-05-08 | 1992-02-18 | Lever Brothers Company, Division Of Conopco, Inc. | Cleaning compositions with bleach-stable colorant |
| JP2594404B2 (en) * | 1992-12-22 | 1997-03-26 | 花王株式会社 | Liquid bleach composition |
| CN1063782C (en) * | 1993-12-29 | 2001-03-28 | 赖基特和科曼公司 | Thickened alkaly metal hypochlorite compositions |
-
1996
- 1996-07-08 MX MX9801081A patent/MX9801081A/en not_active IP Right Cessation
- 1996-07-08 CN CN96196185A patent/CN1102649C/en not_active Expired - Fee Related
- 1996-07-08 AU AU65431/96A patent/AU692718B2/en not_active Ceased
- 1996-07-08 NZ NZ313386A patent/NZ313386A/en unknown
- 1996-07-08 BR BR9609898A patent/BR9609898A/en not_active Application Discontinuation
- 1996-07-08 WO PCT/US1996/011409 patent/WO1997006233A1/en not_active Application Discontinuation
- 1996-07-08 CA CA002228674A patent/CA2228674C/en not_active Expired - Fee Related
- 1996-07-08 EP EP96925280A patent/EP0859826A4/en not_active Withdrawn
- 1996-08-09 IN IN1429CA1996 patent/IN189237B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1102649C (en) | 2003-03-05 |
| EP0859826A1 (en) | 1998-08-26 |
| CN1192775A (en) | 1998-09-09 |
| NZ313386A (en) | 1998-07-28 |
| AU692718B2 (en) | 1998-06-11 |
| EP0859826A4 (en) | 1999-11-24 |
| BR9609898A (en) | 1999-05-25 |
| MX9801081A (en) | 1998-04-30 |
| IN189237B (en) | 2003-01-11 |
| CA2228674A1 (en) | 1997-02-20 |
| AU6543196A (en) | 1997-03-05 |
| WO1997006233A1 (en) | 1997-02-20 |
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