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

Definitions

• This invention relates to thickened liquid bleach-containing compositions useful for hard surface cleaning, and particular to such compositions which include bleach-stable pigments.
• Thickened bleach compositions possess a number of advantages over unthickened bleach compositions.
• 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 ofthe composition must be considered.
• alkali metal hypochlorite degradation may be illustrated by the following equation:
• bleach-containing 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 suggests the use of certain halogenated copper phthalocyanine pigments for aqueous alkali metal hypochlorite compositions. While this class of pigments is considered to be bleach-stable, slow degradation ofthe pigment molecule releases copper which catalyzes the degradation of hypochlorite.
• U.S. Patent No. 4,271,030 (Brierley) describes a suspension of ultramarine blue using calcium soap floes. Use of calcium soap floes is not desirable due to the high concentration required, 50% by volume ofthe composition, or from a cleaning standpoint due to a tendency to precipitate onto hard surfaces.
• This invention provides thickened hypochlorite compositions with enhanced rheological properties which are capable of stably suspending inorganic pigments.
• the thickening system is a blend of surfactants and clay that is rheopectic at low 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.
• 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 utilized include ultramarine blue, cobalt aluminate blue, titanium 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 compared 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%, ofthe formula as compared to other structured liquids, some of which are known in the category of liquid laundry detergents. This characteristic helps to solve the problem of pigment sedimentation while still maintaining thin fluid flow properties which help to achieve good surface coverage for products such as liquid toilet bowl cleaners.
• the composition also has good phase-stability and hypochlorite-stability.
• compositions of this invention comprise:
• an alkali metal salt preferably sodium chloride
• a pH stabilizer to provide a pH of 11 or higher
• the viscosity ofthe composition can range from about 200 cps to about 1000 cps.
• the preferred range is from about 300 - 500 cps.
• Figures 1 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 formulation according to this insertion ( Figure 3) and comparable properties of a similar composition without the clay ( Figure 4).
• 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 agent for stain and soil removal as well as disinfection.
• the high level of hypochlorite stability and single solution phase behaviour ofthe composition enables the composition to have an acceptable shelf life.
• the compositions include also an organic pigment in suspension. In these pigmented compositions, the colour stability, particularly where the pigment is ultramarine blue, is uniquely advantageous.
• the alkali metal ofthe alkali metal hypochlorite is selected from lithium, potassium or sodium.
• sodium hypochlorite is currently preferred.
• the alkali metal hypochlorite may have other by-products ofthe manufacturing process present without adversely affecting the composition.
• the amount of alkali metal hypochlorite employed is within the range of about 0.5 weight % to about 10 weight %, preferably from 1.0 weight % to 5.0 weight %, and more preferably from 1.5 weight % to 3.0 weight %.
• Bentonite clay is a colloidal hydrated aluminum silicate clay found in North America. It consists principally of montmorillonite (Al2 ⁇ 3»4Si ⁇ 2»H2 ⁇ ) 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 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 1.5 weight %, preferably from 0.25 weight % to 1.0 weight %.
• the tertiary amine oxide is ofthe formula:
• R 1 is an alkyl group containing from about 10 to about 16 carbon atoms and each of R 2 and R 3 is a lower alkyl group containing from 1 to 3 carbon atoms.
• R 1 , R 2 and R 3 may be a straight or branched chain; R 1 may contain an odd or an even number of carbon atoms.
• Amine oxides of mixed chain length may be used, which may contain a predominance of one or more chain lengths.
• the tertiary amine oxide is selected from myristyldimethylamine oxide, lauryldimethylamine oxide, and mixtures thereof. Most preferably employed is myristyldimethylamine oxide.
• the amount ofthe tertiary amine oxide employed is preferably 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.
• 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” ofthe solution (where the surfactants become insoluble in water).
• sodium chloride the preferred amount is in the range of about 0.25 weight % to about 2.0 weight %, preferably from 0.5 weight % to 1.5 weight %.
• An alkali metal hydroxide is the preferred pH stabilizer included in the composition, although any pH stabilizer may be employed as long as the stability and viscosity ofthe composition are not adversely affected.
• the alkali metal of 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 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.
• alkali metal alkyl sarcosinate may be represented by the formula: CH 3
• R 4 is a branched or straight chain C10-C16 alkyl group and M is an alkali metal cation (such as lithium, potassium or sodium).
• Sodium lauroyl sarcosinate is most preferred.
• 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 alkali metal C 10 to C 14 straight chain alkylbenzene sulphonate is preferably defined wherein the alkali metal is potassium, lithium, or sodium. Most preferably employed is sodium dodecylbenzene sulphonate.
• the amount of sulphonate used is within the range of from about 0.08 weight % to about 0.8 weight %, more preferably from 0.1 weight % to 0.5 weight %, and most preferably from 0.15 weight % to 0.4 weight %.
• the preferred pigment is ultramarine blue which is an inorganic silicate.
• this material is inert to hypochlorite oxidation and does not catalyze decomposition of hypochlorite, it is insoluble and 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 of this invention provides excellent suspension for ultramarine blue pigment particles.
• 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 ofthe tertiary amine oxide to alkali metal alkylbenzene sulphonate should fall within the range of from about 5:1 to about 11 : 1.
• 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.
• the primary interaction is between the clay and the amine oxide components ofthe formula.
• the combination ofthe clay, sodium chloride, and the sodium hydroxide in solution causes the clay platelets to align in an edge-to-face structure.
• Some ofthe amine oxide acts to stabilize the structure through both ionic and steric interaction.
• Sulphonate and sarcosinate surfactants combine with the remaining amine oxide to form organic structures or micelles which boost viscosity. It is further theorized that these micelles interact with the clay structure to develop the unique rheology ofthe composition.
• This invention provides a commercially advantageous coloured thickening 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.
• Example 1 A blue-pigmented hand surface cleaner was prepared which had the following ingredients, all percentages being by weight.
• Ingredient 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 prepared by dispensing in the main vessel (1) 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.
• a separate vessel (2) sodium chloride and a 25% solution of sodium hydroxide were dissolved in water. The contents of vessel (2) were added to vessel (1) with high agitation.
• FIG. 1 The thixotropic character is evident at 50 sec -1 .
• Figure 2 captures the stress growth 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.
• Comparative Example A cleaning composition containing ultramarine blue pigment, but without bentonite clay was prepared, and the pigment-settling characteristics were compared with the composition ofExample 1.
• the comparative composition was prepared using the method ofExample 1. The two compositions were maintained in a quiescent state for a period of six weeks at 40°C.
• the following table shows the ingredients ofthe compositions and the relevant rheological data.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Biological Depolymerization Polymers (AREA)

Priority Applications (6)

Applications Claiming Priority (4)

Publications (1)

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Family Applications (1)

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Cited By (13)

Citations (7)

Family Cites Families (1)

• 1996
  • 1996-07-08 BR BR9609898A patent/BR9609898A/pt not_active Application Discontinuation
  • 1996-07-08 EP EP96925280A patent/EP0859826A4/en not_active Withdrawn
  • 1996-07-08 AU AU65431/96A patent/AU692718B2/en not_active Ceased
  • 1996-07-08 CN CN96196185A patent/CN1102649C/zh not_active Expired - Fee Related
  • 1996-07-08 NZ NZ313386A patent/NZ313386A/en unknown
  • 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 MX MX9801081A patent/MX9801081A/es not_active IP Right Cessation
  • 1996-08-09 IN IN1429CA1996 patent/IN189237B/en unknown

Patent Citations (7)

Non-Patent Citations (1)

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