AU704639B2 - Concentrated system based on a thickening agent, the said system being dispersible and thickenable by dilution in aqueous medium - Google Patents
Concentrated system based on a thickening agent, the said system being dispersible and thickenable by dilution in aqueous medium Download PDFInfo
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- AU704639B2 AU704639B2 AU21833/95A AU2183395A AU704639B2 AU 704639 B2 AU704639 B2 AU 704639B2 AU 21833/95 A AU21833/95 A AU 21833/95A AU 2183395 A AU2183395 A AU 2183395A AU 704639 B2 AU704639 B2 AU 704639B2
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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
- C11D3/43—Solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
- A23D7/0053—Compositions other than spreads
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/33—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from molasses
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/08—Clay-free compositions containing natural organic compounds, e.g. polysaccharides, or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/08—Clay-free compositions containing natural organic compounds, e.g. polysaccharides, or derivatives thereof
- C09K8/10—Cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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- Agricultural Chemicals And Associated Chemicals (AREA)
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- Coloring Foods And Improving Nutritive Qualities (AREA)
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Description
2 thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being of the order of 60/40 to 99.5/0.5, preferably of the order of 80/20 to 99/1 a polar constituent (Pol) introduced into the said system (Syst) by means of at least one of the constituents of the said system (Syst) in a quantity making it possible to solubilize at least 1 by weight of the organic acid salt (Salt) but not more than 80 S. and preferably of the order of 5 to 50 of the said organic acid salt (Salt) and optionally of the order of 0.5 to 15 by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium.
"Apolar suspension medium or apolar carrier (ApoC)" is intended to mean any constituent which is liquid at the temperature of preparation or use of the said system, which, when situated in the Hansen solubility space (Handbook of solubility parameters and other cohesion parameters Allan F.M. Barton, CRC Press Inc., 1983), exhibits the following parameters: 6P of Keesom interactions lower than 10 (J/cm 3 6H of hydrogen bonds lower than 10 (J/cm 3 6D of London interactions higher than 15 (J/cm 3 By way of examples of apolar suspension medium or apolar carrier (ApoC) there may be mentioned: triglycerides of saturated or unsaturated fatty acids containing at least 12 carbon atoms and preferably from 14 to 20 carbon atoms; these may be synthetic or, preferably, natural triglycerides such as vegetable oils typified by rapeseed oil, soya oil, groundnut oil, butter oil, cottonseed oil, linseed oil, coconut oil, olive oil, palm oil, grapeseed oil, fish oil, castor oil and copra oil, aromatic petroleum cuts, terpenic compounds (D-limonene, L-limonene etc.), mixtures of dimethyl succinate/adipate/glutarate S" diesters, aliphatic hydrocarbons containing at least 6 carbon atoms (isooctane, kerosene, petrol, diesel fuel, mineral oils, lubricating oils etc.).
As an agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media particular mention may be made of polysaccharides of bacterial origin (xanthan gum, succinoglucan, rhamsam, welan, gellan etc.), galactomannans (guar gums and their derivatives, carob, tara etc.), carrageenans, alginates, carboxymethyl celluloses, methyl celluloses, hydroxypropyl celluloses, hydroxyethyl celluloses, alkali metal polyacrylates, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidones etc., by themselves or in mutual combination.
A "multichain" surfactant is intended to mean any surfactant consisting of at least two hydrophobic chains joined by means of a hydrophilic head.
As examples, there may be mentioned alkali metal dialkyl sulphosuccinates such as sodium di(2-ethylhexyl) sulphosuccinate (two octyl chains joined by the sodium sulphosuccinate hydrophilic head), alkaline-earth metal alkylarylsulphonates such as calcium dodecylbenzenesulphonate (two dodecylbenzene chains joined by the Ca disulphonate hydrophilic head), phospholipids, such as phosphatidylcholine, lysophosphatidylcholine, phosphatidylethanolamine or S. phosphatidylinositol, which are present in lecithins of animal origin (egg) or of plant origin (soya etc.), sugar glycerides etc.
The term "sugar glyceride" is intended to mean the mixture obtained by transesterification of sucrose and of triglycerides of saturated or unsaturated fatty acids containing at least 12 carbon atoms and preferably from 14 to 20 carbon atoms; these may be synthetic or preferably natural triglycerides, such as vegetable or animal oils typified by rapeseed oil, soya oil, lard, tallow, groundnut oil, butter oil, cottonseed oil, linseed oil, coconut oil, olive oil, palm oil, grapeseed oil, fish oil, castor oil and copra oil. They are preferably sugar glycerides of lard, of tallow or of palm, copra or rapeseed oil. They are in a liquid form or in the form of more or less consistent pastes differing commercially in their melting point. A method of preparation of sugar glycerides is described especially in Patent Application FR-A-2,463,512.
Among the organic acid salts (Salt) which are not soluble in the apolar medium there may be mentioned alkali metal or ammonium salts of aliphatic or aromatic carboxylic acids, such as sodium benzoate, sodium propionate, sodium acetate etc.
By way of agent thickening apolar media (ApoTh) very particular mention may be made of their combinations: sodium dioctyl sulphosuccinate/sodium benzoate, sodium dioctyl sulphosuccinate/sodium propionate, sodium dioctyl sulphosuccinate/sodium acetate, calcium dodecylbenzenesulphonate/sodium benzoate, lecithin/sodium benzoate, sugar glycerides/sodium benzoate, sugar glycerides/sodium propionate, sugar glycerides/sodium acetate, lecithin/sodium benzoate, lecithin/sodium propionate and lecithin/sodium acetate.
As an example of agent capable of emulsifying the said apolar medium in water or in an aqueous medium there may be mentioned ethoxylated tristyrylphenols, ethoxylated and/or propoxylated tristyrylphenol sulphates or phosphates, ethoxylated and/or propoxylated fatty acids or alcohols and ethoxylated/propoxylated block copolymers.
"Polar compound" (Pol) is intended to mean any constituent which is liquid at the temperature of 6 preparation or use of the said system, which, when situated in the Hansen solubility space, has the following parameters: 6P of Keesom interactions higher than 8 (J/cm 3 6H of hydrogen bonds higher than 17 (J/cm 3 6D of London interactions of between 13 and 17 (J/cm 3 )V2 Among these there may be mentioned water, formamide, glycerol, ethanol etc.
The preferred polar compound is water; this is introduced by means of at least one of the constituents of the system, especially by means of the agent thickening apolar media (ApoTh).
The said system forming the subject matter of a, the invention may additionally contain various additives, especially additives which are not soluble in the apolar suspension medium, such as fillers of the silica, calcium carbonate and similar type, watersoluble basic compounds such as sodium metasilicates, 20 clays, alkali metal phosphates, solid sodium hydroxide and the like.
The said system in apolar medium (Syst), forming the subject matter of the invention, may be prepared in two stages: a first stage consisting in placing the apolar carrier (ApoC) in contact with the agent thickening apolar media (ApoTh) containing the polar constituent (Pol), then a second stage, consisting in introducing into the mixture thus obtained the agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, the optional emulsifier being preferably introduced in the first stage.
A preferred method of carrying out the first stage consists in introducing into the apolar carrier (ApoC), heated to a temperature of the order of 30 to 100°C, generally of the order of 50 to 80°C, the required quantity of agent thickening apolar media (ApoTh) and the optional emulsifier, and in dispersing the whole with the aid of a homogenizer.
For this stage to be well carried out, the 15 agent thickening apolar media (ApoTh) containing the polar constituent (Pol) is prepared beforehand by homogenizing a mixture of the "multichain" surfactant (SA) and of a solution of the organic acid salt (Salt) in the polar constituent (Pol), and then evaporation of 20 the excess quantity of polar constituent (Pol).
The second stage is favourably carried out at a temperature of the order of 30 to 80°C by introducing into the thickened medium prepared in the first stage the required quantity of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, with stirring with the aid of a device of the deflocculator blade type.
Depending on the nature and the relative 8 quantities of its various constituents, the system forming the subjectmatter of the invention may be used, after dilution in water or in an aqueous medium, for the formulation of water-based drilling fluids, especially as a fluid for tunnelling, for the preparation of molasses usable in feedstuffs or foodstuffs or as industrial cleaning agent.
Another subject of the invention consists therefore of a specific system usable in particular, after dilution in water for the formulation of waterbased drilling fluid.
The said system in apolar medium (Syst Sl) usable for the formulation of water-based drilling fluid is characterized in that it includes: 15 of the order of 40 to 70 preferably of the order of 50 to 60 by weight of an apolar suspension medium or apolar carrier (ApoC) of the order of 20 to 50 preferably of the order of 25 to 45 by weight of at least one agent 20 capable of thickening aqueous media (AqTh) but not capable of thickening apolar media of the order of 0.5 to 5 preferably of the order of 1.5 to 4 by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), 9 the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being of the order of 60/40 to 99.5/0.5, preferably of the order of 80/20 to 99/1, a polar constituent (Pol) introduced into the said system (Syst Sl) by means of at least one of the constituents of the said system (Syst Sl) in a quantity making it possible to solubilize at least 1 by weight of the organic acid salt (Salt) but not more than 80 preferably of the order of 5 to 50 of the said organic acid salt (Salt), optionally of the order of 1 to 10 by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium.
The constituents which may form part of the 15 compositions of the said system (Syst Sl) are those already mentioned above in relation to the general system (Syst) One system (Syst S'1) usable for the formulation of water-based drilling fluid and very 20 particularly advantageous because of its respect for the environment is that including: of the order of 40 to 70 preferably of :the order of 50 to 60 by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from natural triglycerides, of the order of 20 to 50 preferably of the order of 25 to 45 by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, chosen from polysaccharides of bacterial origin, galactomannans, carrageenans, alginates, carboxymethyl celluloses, methyl celluloses, hydroxypropyl celluloses and hydroxyethyl celluloses, of the order of 0.5 to 5 preferably of the order of 1.5 to 4 by weight of at least one agent thickening apolar media (ApoTh) consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC), chosen from alkali metal dialkyl sulphosuccinates, alkaline-earth metal alkylarylsulphonates, phospholipids, sugar glycerides, and of an organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), chosen from 15 sodium benzoate, sodium propionate and sodium acetate, the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being of the order of 60/40 to 99.5/0.5, preferably of the order of 80/20 to 99/1, e water as polar constituent (Pol), 20 introduced into the said system (Syst S'1) by means of at least one of the constituents of the said system (Syst in a quantity making it possible to solubilize at least 1 by weight of the organic acid salt (Salt) but not more than 80 preferably of the order of 5 to 50 of the said organic acid salt (Salt), and optionally of the order of 1 to 10 by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium, chosen from ethoxylated and/or propoxylated fatty acids or alcohols.
Among the natural triglycerides forming the apolar carrier (ApoC) there may be mentioned vegetable oils typified by rapeseed oil, soya oil, groundnut oil, butter oil, cottonseed oil, linseed oil, coconut oil, olive oil, palm oil, grapeseed oil, fish oil, castor oil and copra oil.
Among the polysaccharides of bacterial origin which are capable of thickening aqueous media (AqTh) there may be mentioned xanthan gum, succinoglucan, rhamsan, welan, gellan etc.; guar, carob, tara and similar gums may be mentioned among galactomannans.
15 The systems (Syst S1 and S'1) forming the subjectmatter of the invention may next be diluted in water or in an aqueous medium until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, 20 introduced by means of the said system (Syst S1 or which is of the order of 0.01 to 3, preferably of the order of 0.01 to 1 part by weight, in 100 parts by weight of water.
Another subject of the invention also consists of a system in apolar medium (Syst S2) which can be applied to the preparation of molasses usable in feedstuffs or foodstuffs.
The said system in apolar medium (Syst S2) is characterized in that it includes: of the order of 40 to 70 preferably of the order of 50 to 60 by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from natural triglycerides, of the order of 20 to 50 preferably of the order of 30 to 40 by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, chosen from xanthan gum, galactomannans, carrageenans and alginates, of the order of 1 to 10 preferably of the order of 2 to 7 by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is 15 soluble or dispersible in the apolar carrier (ApoC), chosen from lecithins and sugar glycerides, and of sodium benzoate as organic acid salt (Salt) which is S* not soluble in the apolar carrier (ApoC), the weight ratio of "multichain" surfactant 20 (SA)/organic salt (Salt) being of the order of 60/40 to 99.5/0.5, preferably of the order of 80/20 to 99/1, and of water as polar constituent (Pol), e* introduced into the said system (Syst S2) by means of at least one of the constituents of the said system (Syst S2), in a quantity making it possible to solubilize at least 1 by weight of the organic acid salt (Salt) but not more than 80 preferably of the order of 5 to 50 of the said organic acid salt (Salt).
Among the natural triglycerides forming the apolar carrier (ApoC) there may be mentioned vegetable oils typified by rapeseed oil, soya oil, groundnut oil, butter oil, cottonseed oil, linseed oil, coconut oil, olive oil, palm oil, grapeseed oil, fish oil, castor oil and copra oil.
The system (Syst S2) forming the subjectmatter of the invention may next be diluted in water or in an aqueous medium until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, introduced by means of the said system (Syst S2), which is of the order of 0.01 to 3, preferably of the order of 0.01 to 15 2 parts by weight, in 100 parts of water.
**too: The invention also has as its subjectmatter a system in apolar medium (Syst S3) usable as industrial .f cleaning agent, after dilution in water or in an aqueous medium.
S. 20 The said system in apolar medium (Syst S3) is characterized in that it includes: of the order of 60 to 90 preferably of the order of 70 to 80 by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from active solvents for fats or for soiling of animal origin, of the order of 2 to 20 preferably of the order of 5 to 10 by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, of the order of 2 to 20 preferably of the order of 5 to 10 by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the polar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being of the order of 60/40 to 99.5/0.5, preferably of the order of 80/20 to 99/1, a polar constituent (Pol) introduced into the said system (Syst S3) by means of at least one of S 15 the constituents of the said system (Syst S3) in a to quantity making it possible to solubilize at least 1 :by weight of the organic acid salt (Salt) but not more than 80 preferably of the order of 5 to 50 of the said organic acid salt (Salt), a and optionally of the order of 0.5 to 15 by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium.
By way of example of active solvent there may be mentioned terpenic compounds such as D-limonene, petroleum cuts, aliphatic hydrocarbons (petrol), mixtures of dimethyl succinate/adipate/glutarate diesters etc.
The other constituents which may form part of the compositions of the said system (Syst S3) are those already mentioned above in relation to the general system (Syst).
The system (Syst S3) forming the subjectmatter of the invention may subsequently be diluted in water or in an aqueous medium until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, introduced by means of the said system (Syst 53), which is of the order of 0.1 to 1, preferably of the order of 0.2 to 0.5 parts by weight, in 100 parts of water.
The said system self-emulsifies in the medium which thickens to a Brookfield viscosity value of the 15 order of 800 to 900 mPa s, the viscosity being measured with the aid of a Brookfield viscometer at revolutions/minute with the aid of spindle No. 2 at 0
C.
After being thrown onto a vertical surface the emulsion flows slowly. This emulsion can favourably be employed for the degreasing or cleaning of surfaces in slaughterhouses for animals, poultry, in industrial grill-rooms, etc.
The following examples are given by way of illustration.
Example 1 General procedure for the preparation of the concentrated system in apolar medium (Syst) The apolar carrier (ApoC) is placed in a 1-litre container and then heated to a temperature close to 800C.
The required quantity of thickening agent (ApoTh) for the apolar medium, prepared beforehand, is introduced into the medium, as well as the optional agent capable of emulsifying the apolar carrier in water; the whole is dispersed with the aid of a Rayneri deflocculator blade marketed by Rayneri, rotating at 400 revolutions/minute for 1 minute, and then homogenized with the aid of an Ultra-Turrax 15 (marketed by Ultra-Turrax) of 670-W power and rotating at 8,000 revolutions/minute, for 7 minutes. The final temperature of the medium is of the order of 100°C.
The medium is allowed to cool to a temperature of the order of 80 0 C and the required quantity of agent thickening aqueous media (AqTh) is then added to the thickened medium thus obtained, with stirring with the aid of a Rayneri deflocculator blade rotating at 500 revolutions/minute; the stirring is continued for 5 minutes.
Operatin procedure for preparation of the thickening mixture (ApoTh) for the apolar carrier The "multichain" surfactant (SA) and an aqueous solution of organic acid salt (Salt) are introduced into a 500-ml container; the mixture is homogenized by stirring with the aid of a Rayneri® deflocculator blade rotating at 400 revolutions/minute.
The excess water is subsequently evaporated.
Thus, a thickening mixture consisting of sodium dioctyl sulphosuccinate, of sodium benzoate and of water is prepared as indicated above, from approximately 63 parts by weight of sodium dioctyl sulphosuccinate and of approximately 37 parts of an aqueous solution containing 30 by weight of sodium benzoate. The excess water is evaporated off to a residual water content making it possible to solubilize approximately 10 by weight of sodium benzoate.
SExample 2 S 15 Concentrated system in apolar medium thickening on dilution, for the drilling fluid formulation The following system is prepared according to the procedure described in Example 1: ingredients by weight 20 rapeseed oil 53.35 sodium dioctyl sulphosuccinate 1.35 sodium benzoate 0.25 water 0.05 xanthan The system obtained is dispersed in water in a quantity which makes it possible to obtain a dilute medium which has a xanthan gum concentration of 0.5 18 by weight.
Figure 1 shows that the variation in dynamic viscosity of the medium obtained as a function of the rate gradient, measured with the aid of the Rheomat 115 marketed by Contraves, is practically similar to that of a solution of xanthan gum at a concentration of 0.5 in water.
The dispersion obtained is therefore pumpable.
Example 3 Concentrated system in apolar medium thickening on dilution, for the formulation of molasses useful in feedstuffs or foodstuffs .The following system is prepared according to the procedure described in Example 1: ingredients by weight rapeseed oil 54.9 soya lecithin 4.25 sodium benzoate 0.75 20 water 0.1 xanthan The system obtained is dispersed in water in a quantity which makes it possible to obtain a dilute medium which has a xanthan gum concentration of 0.3 by weight.
The dispersion obtained is pumpable.
Example 4 Concentrated system in apolar medium thickening on dilution, for industrial cleaning The following system is prepared according to the procedure described in Example 1: ingredients by weight D-limonene 78.3 sodium dioctyl sulphosuccinate 6.6 sodium benzoate 1.2 water 0.2 xanthan isodecyl alcohol ethoxylated with 6 moles of OE 7.7 The concentrate is diluted in mains water so 15 as to obtain a concentration of 0.3 of xanthan gum.
:An emulsion forms instantly; it thickens and exhibits a Brookfield viscosity, measured at revolutions/min with the aid of spindle No. 2 at 25°C of the order of 800 to 900 mPa s.
The dispersion obtained is pumpable.
After spraying onto a vertical or sloping surface it flows off slowly, which allows a maximum degreasing of the surface.
THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:- 1. Concentrated system in apolar medium (Syst), including: 40 to 90% by weight of an apolar suspension medium or apolar carrier (ApoC), 0.5 to 55% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, 0.5 to 15% by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being 60/40 to 99.5/0.5, a polar constituent (Pol) introduced into the said system (Syst) by means of at least one of the constituents of the said system (Syst) in a quantity making it possible to solubilize at least 1% by weight of the organic acid salt (Salt) but not more than 80%, of the said organic acid salt (Salt), 2. A concentrated system according to Claim 1 further including: 0.5 to 15% by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium.
3. A concentrated system according to Claim 1 or Claim 2 including 45 to 80% by weight of an apolar suspension medium or apolar carrier (ApoC).
4. A concentrated system according to any one of the preceding claims including 2 to 50% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media.
A concentrated system according to any one of the preceding claims including 1 to 10% by weight of at least one agent thickening apolar media (ApoTh).
6. A concentrated system according to any one of the preceding claims wherein the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) is 80/20 to 99/1.
7. A concentrated system according to any one of the preceding claims including a polar constituent (Pol) in a quantity making it possible to solubilize 5 to of said organic acid salt (Salt).
F-
-21 8. Concentrated system according to any one of the preceding claims wherein the apolar carrier (ApoC) is chosen from triglycerides of saturated or unsaturated fatty acids containing at least 12 carbon atoms, aromatic petroleum cuts, terpenic compounds, mixtures of dimethyl succinate/adipate/glutarate diesters and aliphatic hydrocarbons containing at least 6 carbon atoms.
9. A concentrated system according to Claim 8 wherein the saturated or unsaturated fatty acids contain 14 to 20 carbon atoms.
Concentrated system in apolar medium, according to any one of the preceding claims wherein the agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, is chosen from polysaccharides of bacterial origin, galactomannans, carrageenans, alginates, carboxymethyl celluloses, methyl celluloses, hydroxypropyl celluloses, hydroxyethyl celluloses, alkali metal polyacrylates, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidones, by themselves or in mutual Scombination.
11. Concentrated system in apolar medium, according to any one of the preceding claims wherein the "multichain" surfactant (SA) is chosen from alkali metal dialkyl sulphosuccinates, alkaline-earth metal alkylarylsulphonates, phospholipids and S* sugar glycerides.
S* 12. Concentrated system in apolar medium, according to any one of the preceding claims wherein the organic acid salt (Salt) which is not soluble in the polar medium is an alkali metal or ammonium salt of aliphatic or aromatic carboxylic acids.
13. Concentrated system in apolar medium, according to any one of the preceding claims wherein the agent thickening apolar media (ApoTh) is chosen from the combinations: sodium dioctyl sulphosuccinate/sodium benzoate, sodium dioctyl sulphosuccinate/sodium propionate, sodium dioctyl sulphosuccinate/sodium acetate, calcium dodecylbenzenesulphonate/sodium benzoate, lecithin/sodium benzoate, sugar glycerides/sodium benzoate, sugar glycerides/sodium propionate, sugar glycerides/ sodium acetate, lecithin/sodium benzoate, lecithin/sodium propionate and lecithin/sodium acetate.
Claims (3)
14. Concentrated system in apolar medium, according to any one of the preceding claims wherein the polar compound (Pol) is chosen from water, formamide, glycerol and ethanol. Concentrated system in apolar medium, according to Claim 14 wherein the polar compound (Pol) is water introduced by means of the agent thickening apolar media (ApoTh).
16. Concentrated system in apolar medium, according to any one of the preceding claims wherein the agent capable of emulsifying the said apolar medium in water or in an aqueous medium is chosen from ethoxylated tristyrylphenols, ethoxylated and/or propoxylated tristyrylphenol sulphates or phosphates, ethoxylated and/or propoxylated fatty acids or alcohols and ethoxylated/propoxylated block copolymers. S* 17. System in apolar medium (Syst Si), according to any one of the .i preceding claims, usable for the formulation of water-based drilling fluid, including: 40 to 70% by weight of an apolar suspension medium or apolar carrier (ApoC), 20 to 50% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, 0.5 to 5% by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible 0* in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being 60/40 to
99.5/0.5, a polar constituent (Pol) introduced into the said system (Syst S 1) by means of at least one of the constituents of the said system (Syst S1) in a quantity making it possible to solubilize at least 1% by weight of the organic acid salt (Salt) but not more than 80% of the said organic acid salt (Salt), 18. A system according to Claim 17 further including: 1 to 10% by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium. 19. A system according to Claim 17 or Claim 18 including 50 to 60% by weight of an apolar suspension medium or apolar carrier (ApoC). -23- A system according to any one of Claims 17 to 19 including 25 to by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media. 21. A system according to any one of Claims 17 to 20 including 1.5 to 4% by weight of at least one agent thickening apolar media (ApoTh). 22. A system according to any one of Claims 17 to 21 wherein the weight ratio of"multichain" surfactant (SA)/organic salt (Salt) is 80/20 to 99/1. 23. A system according to any one of Claims 17 to 22 including a polar constituent (Pol) in a quantity making it possible to solubilize at 5 to 50% of the said organic acid salt (Salt). 24. Concentrated system in apolar medium (Syst according to any one of Claims 17 to 23, usable for the formulation of water-based drilling fluid, including: 40 to 70% by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from natural triglycerides, 20 to 50% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, chosen from polysaccharides of bacterial origin, galactomannans, carrageenans, alginates, carboxymethyl celluloses, methyl celluloses, hydroxypropyl celluloses and hydroxyethyl celluloses, 0.5 to 5% by weight of at least one agent thickening apolar media (ApoTh) consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC), chosen from alkali metal dialkyl sulphosuccinates, alkaline- earth metal alkylarylsulphonates, phospholipids, sugar glycerides, and of an organic acid *S salt (Salt) which is not soluble in the apolar carrier (ApoC), chosen from sodium benzoate, sodium propionate and sodium acetate, the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being 60/40 to 99.5/0.5, water as polar constituent (Pol), introduced into the said system (Syst S'1) by means of at least one of the constituents of the said system (Syst in a quantity making it possible to solubilize at least 1% by weight of the organic acid salt (Salt) but not more than 80% of the said organic acid salt (Salt), -24- A concentrated system according to Claim 24 further including: 1 to 10% by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium, chosen from ethoxylated and/or propoxylated fatty acids or alcohols. 26. A concentrated system in apolar medium (Syst S' according to Claim 24 or Claim 25 including 50-60% by weight of an apolar suspension medium or apolar carrier (ApoC). 27. A concentrated system in apolar medium (Syst S'1) according to any one of Claims 24 to 26 including 25 to 45% by weight of at least one agent capable of i, thickening aqueous media (AqTh) but not capable of thickening apolar media. 28. A concentrated system in apolar medium (Syst S'1) according to any one S. of Claims 24 to 27 including 1.5 to 4% by weight of at least one agent thickening apolar media (ApoTh). 29. A concentrated system in apolar medium (Syst S'1) according to any one of Claims 24 to 28 wherein the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) is 80/20 to 99/1. A concentrated system in apolar medium (Syst S'1) according to any one of Claims 24 to 29 including water as a polar constituent (Pol) in a quantity making it possible to solubilize 5 to 50% of the said organic acid salt (Salt). 31. Concentrated system in apolar medium (Syst S2), according to Claim 1, usable for the preparation of molasses for feedstuffs or foodstuffs, including: 40 to 70% by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from natural triglycerides, 20 to 50% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, chosen from xanthan gum, galactomannans, carrageenans and alginates, 1 to 10% by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC), chosen from lecithins and sugar glycerides, and of sodium benzoate as organic acid salt (Salt) which is not soluble in the apolar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being 60/40 to 99.5/0.5, 0* 0 0* *SS@ 0* 0S 0 *OS@ @0 0 00 0 *0 0 *0 S 0 0 0S and of water as polar constituent (Pol), introduced into the said system (Syst S2) by means of at least one of the constituents of the said system (Syst S2), in a quantity making it possible to solubilize at least 1% by weight of the organic acid salt (Salt) but not more than 80% of the said organic acid salt (Salt). 32. A concentrated system according to Claim 31 including 50 to 60% by weight of an apolar suspension medium or apolar carrier (ApoC). 33. A concentrated system according to Claim 31 or Claim 32 including 30 to by weight of at least one agent capable of thickening aqueous media but not capable of thickening apolar media. 34. A concentrated system according to any one of the Claims 31 to 33 including 2 to 7% by weight of at least one agent thickening apolar media (ApoTh). A concentrated system according to any one of the Claims 31 to 34 wherein the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) is of the order of 80/20 to 99/1. 36. A concentrated system according to any one of Claims 31 to 35 including water as a polar constituent in a quantity making it possible to solubilize 5 to 50% of the said organic acid salt (Salt). 37. Concentrated system in apolar medium (Syst S3) according to any one of Claims 1 to 7 or any one of Claims 10 to 16, usable as industrial cleaning agent, including: 60 to 90% by weight of an apolar suspension medium or apolar carrier (ApoC) chosen from active solvents for fats or for soiling of animal origin, 2 to 20% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, 2 to 20% by weight of at least one agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC) and of an organic acid salt (Salt) which is not soluble in the polar carrier (ApoC), the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) being 60/40 to 99.5/0.5, -26- a polar constituent (Pol) introduced into the said system (Syst S3) by means of at least one of the constituents of the said system (Syst S3) in a quantity making it possible to solubilize at least 1% by weight of the organic acid salt (Salt) but not more than 80% of the said organic acid salt (Salt), 38. A concentrated system according to Claim 37 further including: 0.5 to 15% by weight of an agent capable of emulsifying the said apolar medium in water or in an aqueous medium. 39. A concentrated system in apolar medium according to Claim 37 or Claim 38 including 70 to 80% by weight of an apolar suspension medium or apolar carrier (ApoC). 40. A concentrated system according to any one of Claims 37 to 39 including 5 to 10% by weight of at least one agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media. 41. A concentrated system according to any one of Claims 37 to 40 including to 10% by weight of at least one agent thickening apolar media (ApoTh). 42. A concentrated system according to any one of Claims 37 to 41 wherein the weight ratio of "multichain" surfactant (SA)/organic salt (Salt) is 80/20 to 99/1. *e S43. A concentrated system according to any one of Claims 37 to 42 including a polar constituent (Pol) in a quantity making it possible to solubilize 5 to 50% of the said organic acid salt (Salt). e 0o 44. Process for the preparation of the concentrated system in apolar medium forming the subject of any one of the preceding claims, characterized in that it includes C two stages: a first stage consisting in placing the apolar carrier (ApoC) in contact with the agent thickening apolar media (ApoTh) containing the polar constituent (Pol), then a second stage, consisting in introducing into the mixture thus obtained the agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media. A process according to Claim 44 wherein the optional emulsifier is introduced in the first stage. -27- 46. Use of the concentrated system in apolar medium (Syst S1 or Syst S'1) as defined in any one of Claims 17 to 30, for the formulation of drilling fluids, after dilution in water or in an aqueous medium, until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, introduced by means of the said system (Syst S1 or which is 0.01 to 3 parts by weight, in 100 parts of water. 47. The use of Claim 46 which is 0.01 to 1 parts by weight, in 100 parts of water. 48. Use of the concentrated system in apolar medium (Syst S2), as defined in i. any one of Claims 31 to 36, for the preparation of molasses for foodstuffs or feedstuffs, after dilution in water or in an aqueous medium, until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar o.i media, introduced by means of the said system (Syst S2), which is 0.01 to 3 parts by S. weight, in 100 parts of water. 49. The use of Claim 48 which is 0.01 to 2 parts by weight, in 100 parts of water. Use of the concentrated system in apolar medium (Syst S3) as defined in any one of Claims 37 to 43, as industrial cleaning agent, after dilution in water or in an aqueous medium, until a concentration is obtained of agent capable of thickening aqueous media (AqTh) but not capable of thickening apolar media, introduced by means of the said system (Syst S3), which is 0.1 to 1 parts by weight, in 100 parts of water. 51. The use of Claim 50 which is 0.2 to 0.5 parts by weight, in 100 parts of water. 52. A concentrated system in apolar medium, substantially as herein described with reference to any one of the Examples. 53. A process for the preparation of a concentrated system in apolar medium, substantially as herein described with reference to any one of the Examples. DATED this 22nd day of February 1999 RHONE-POULENC CHIMIE Attorney: PAUL G. HARRISON Fellow Institute of Patent Attorneys of Australia of BALDWIN SHELSTON WATERS ABSTRACT Concentrated system in apolar medium (Syst), including: an apolar carrier (ApoC), an agent capable of thickening aqueous media (AqTh), but not capable of thickening apolar media, an agent thickening apolar media (ApoTh), consisting of a mixture of a "multichain" surfactant (SA) which is soluble or dispersible in the apolar carrier (ApoC), and of an organic salt (Salt) which is not soluble in the apolar carrier (ApoC), a polar constituent (Pol) introduced into the said system (Syst) by means of at least one of the 15 constituents of the said system (Syst) in a quantity 0 making it possible to solubilize at least 1 by weight of the organic acid salt (Salt) but not more than 80 of the said organic acid salt (Salt), optionally an agent capable of emulsifying 20 the said apolar carrier in water or in an aqueous medium. Depending on the nature of its various constituents, the said system may be used, after dilution in water or in an aqueous medium, for the formulation of water-based drilling fluids, for the preparation of molasses usable in feedstuffs or foodstuffs or as an industrial cleaning agent. a a a
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9407660 | 1994-06-22 | ||
FR9407660A FR2721533B1 (en) | 1994-06-22 | 1994-06-22 | Concentrated system based on a thickening agent, said system being dispersible and thickenable by dilution in an aqueous medium. |
Publications (2)
Publication Number | Publication Date |
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AU2183395A AU2183395A (en) | 1996-01-04 |
AU704639B2 true AU704639B2 (en) | 1999-04-29 |
Family
ID=9464517
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU21833/95A Ceased AU704639B2 (en) | 1994-06-22 | 1995-06-21 | Concentrated system based on a thickening agent, the said system being dispersible and thickenable by dilution in aqueous medium |
Country Status (9)
Country | Link |
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EP (1) | EP0688848A1 (en) |
JP (1) | JPH083535A (en) |
KR (1) | KR960000296A (en) |
CN (1) | CN1121518A (en) |
AU (1) | AU704639B2 (en) |
BR (1) | BR9502901A (en) |
CA (1) | CA2152462A1 (en) |
FR (1) | FR2721533B1 (en) |
NO (1) | NO952458L (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2826460B1 (en) * | 2009-07-20 | 2017-08-23 | L'oreal | Emulsion containing a dispersion of bismuth oxychloride |
CN102212358A (en) * | 2010-04-09 | 2011-10-12 | 新疆荣森农业科技有限公司 | Preparation of hydrocarbon-based fracturing fluid thickening agent for oil production |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4631136A (en) * | 1985-02-15 | 1986-12-23 | Jones Iii Reed W | Non-polluting non-toxic drilling fluid compositions and method of preparation |
US5196215A (en) * | 1990-09-20 | 1993-03-23 | Myoshi Oil & Fat Co., Ltd. | Cavity forming agent for edible foods |
US5277836A (en) * | 1992-02-14 | 1994-01-11 | Bio-Safe Specialty Products, Inc. | Terpene cleaning compositions and methods of using the same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52107010A (en) * | 1976-12-17 | 1977-09-08 | Sanei Kagaku Kogyo Kk | Stabilization method of aqueous fat emulsions |
FR2463512A1 (en) | 1979-05-30 | 1981-02-20 | Anvar | Josephson junction device - comprising superconducting or semiconducting strip on insulating substrate and sub-regions sepd. by barrier from the strip |
GB8311854D0 (en) * | 1983-04-29 | 1983-06-02 | Unilever Plc | Detergent compositions |
JPS6014933A (en) * | 1983-07-07 | 1985-01-25 | Lion Corp | Preparation of w/o type emulsion |
GB8813552D0 (en) * | 1988-06-08 | 1988-07-13 | Unilever Plc | Thickening system |
JPH0721154B2 (en) * | 1988-10-15 | 1995-03-08 | 三洋化成工業株式会社 | Cleaning composition |
JP2743442B2 (en) * | 1989-02-28 | 1998-04-22 | 味の素株式会社 | Low viscosity emulsified composition |
JPH03215690A (en) * | 1990-01-18 | 1991-09-20 | Nippon Alpha Metals Kk | Cleaning composition for material to be plated |
JP3116294B2 (en) * | 1992-11-20 | 2000-12-11 | 味の素株式会社 | Liquid detergent composition |
-
1994
- 1994-06-22 FR FR9407660A patent/FR2721533B1/en not_active Expired - Fee Related
-
1995
- 1995-06-16 EP EP95401414A patent/EP0688848A1/en not_active Withdrawn
- 1995-06-20 NO NO952458A patent/NO952458L/en unknown
- 1995-06-21 AU AU21833/95A patent/AU704639B2/en not_active Ceased
- 1995-06-21 JP JP7176920A patent/JPH083535A/en active Pending
- 1995-06-22 KR KR1019950016958A patent/KR960000296A/en not_active Application Discontinuation
- 1995-06-22 CN CN95108322A patent/CN1121518A/en active Pending
- 1995-06-22 CA CA002152462A patent/CA2152462A1/en not_active Abandoned
- 1995-06-22 BR BR9502901A patent/BR9502901A/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4631136A (en) * | 1985-02-15 | 1986-12-23 | Jones Iii Reed W | Non-polluting non-toxic drilling fluid compositions and method of preparation |
US5196215A (en) * | 1990-09-20 | 1993-03-23 | Myoshi Oil & Fat Co., Ltd. | Cavity forming agent for edible foods |
US5277836A (en) * | 1992-02-14 | 1994-01-11 | Bio-Safe Specialty Products, Inc. | Terpene cleaning compositions and methods of using the same |
Also Published As
Publication number | Publication date |
---|---|
KR960000296A (en) | 1996-01-25 |
AU2183395A (en) | 1996-01-04 |
FR2721533B1 (en) | 1996-09-27 |
NO952458D0 (en) | 1995-06-20 |
FR2721533A1 (en) | 1995-12-29 |
BR9502901A (en) | 1996-06-04 |
EP0688848A1 (en) | 1995-12-27 |
NO952458L (en) | 1995-12-27 |
JPH083535A (en) | 1996-01-09 |
CA2152462A1 (en) | 1995-12-23 |
CN1121518A (en) | 1996-05-01 |
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