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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

• This invention relates to an anti-foaming agent granular product which is suited for compounding into powdered detergents for clothing and to a process for producing the same.
• drum type washing machines are predominantly used.
• Detergents to be used in drum type washing machines generally contain an anti-foaming agent because a foam reduces washing efficiency.
• Silicone is a well-known anti-foaming agent which inhibits foaming on washing. Silicon effectively inhibits foaming immediately after being compounded into a powdered detergent but undergoes reduction in anti-foaming effect with time. While silicone is spread on the interface between air and water to exert its anti-foaming effect, when a detergent after storage is mixed with water, silicone is dispersed in an aqueous solution, and its anti-foaming effect cannot be fully manifested.
• silicone is generally compounded into a detergent after being granulated or treated with a coating so that it may not contact directly with detergent components.
• silicone granules obtained by adsorbing silicone onto a builder of detergents, such as sodium sulfate, sodium carbonate, and sodium tripolyphosphate, as a carrier and mixing in the presence of a binder are used.
• JP-A-50-157403 (corresponding to British Patent 1492939) (the term "JP-A” as used herein means an "unexamined published Japanese patent application”) proposes that water-­insoluble starch can be used as the carrier for silicone, and JP-A-61-271007 (corresponding to European Patent 206522) and JP-A-62-57616 (corresponding to U.S. Patent 4,818,292) proposes anti-foaming agent granular product in which preliminarily gelatinized and partially hydrated water-swelling and water-­insoluble starch is used as a carrier.
• the granules are hardly dissolved in cold water-washing condition as in Japan because of water-insolubility of the starch carrier and liable to remain on laundry as an insoluble matter.
• An object of this invention is to provide an silicone-containing anti-foaming agent granular product whose anti-foaming effect is not reduced during storage due to oozing of silicone and which is easily dissolved even in cold water.
• the inventors have conducted extensive investigations and, as a result, found that the above object is accomplished by using a water-soluble starch as a carrier of silicone, thus having reached the present invention.
• the present invention relates to an anti-foaming agent granular product comprising (a) a silicone anti-foaming agent, (b) at least one compound selected from the group consisting of a water-soluble starch, a modified water-soluble starch or a derivative thereof, an (a)/(b) weight ratio being from 0.1 to 0.5 and a total amount of (a) and (b) being from 30 to 80% by weight based on the total weight of the granular product, (c) from 0.5 to 40% by weight, based on the total weight of the granular product, of an inorganic builder or a clay mineral, and (d) from 10 to 40% by weight, based on the total weight of the granular product, of an organic binder having a melting point or a softening point of from 40 to 160°C.
• the present invention further relate to a process for producing the anti-foaming agent granular product.
• the silicone anti-foaming agent which can be used as component (a) in the present invention is not particularly limited.
• polydimethyl­siloxane of the above formula wherein R and R′ each represents a methyl group is suitable.
• the water-soluble starch, the modified water-soluble starch or the derivative thereof which can be used as component (b) in the present invention includes an esterified starch (e.g., starch phosphate), an etherified starch (e.g., carboxymethylated starch), an enzyme-modified dextrin (e.g., maltodextrin), and a roasted dextrin, with the enzyme-modified dextrin (e.g., maltodextrin) and the roasted dextrin being preferred.
• Component (b) serves as a carrier for the silicone anti-foaming agent (a).
• Components (a) and (b) are used at an (a)/(b) weight ratio of from 0.1 to 0.5, and preferably from 0.15 to 0.4.
• An (a)/(b) weight ratio less than 0.1 is economically disadvantageous. If it exceeds 0.5, silicone oozes out and cannot be stably supported by the carrier.
• the total content of components (a) and (b) in the granular product ranges from 30 to 80% by weight, preferably 50 to 80% by weight, more preferably 70 to 80% by weight, based on the total weight of the granular product. A total content less than 30% by weight is economically disadvantageous. If it exceeds 80% by weight, granulation becomes difficult.
• the inorganic builder or clay mineral which can be used as component (c) in the present invention is used as a granulation aid.
• suitable inorganic builders or clay minerals are sulfates, carbonates, bicarbonates, sesquicarbonates, tripolyphosphates, zeolite, and bentonite. Preferred of them are water-soluble builders.
• water-soluable builders include sodium sulfate, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium tripolyphosphate. Among them, sodium saltate is preferred.
• Component (c) is used in an amount of from 0.5 to 40% by weight, and preferably from 3.0 to 30% by weight, based on the total weight of the granular product. If the content of component (c) is less than 0.5% by weight, granulation of silicone-on-carrier becomes difficult.
• a binding aid is used as component (d).
• a binding aid an organic binder having a melting point or a softening point of from 40 to 160°C, and preferably from 45 to 85°C, is employed for maintaining storage stability of granules in high temperatures.
• the organic binder (d) is a nonionic substance.
• suitable organic binders (d) include polyethylene glycol having a molecular weight of from 1,500 to 20,000, polyethylene glycol alkyl ethers having from 8 to 22 carbon atoms in the alkyl moiety thereof, fatty acids containing alkyl group(s) having from 8 to 22 carbon atoms, and ethylene oxide-propylene oxide block copolymers. The most preferred of them is polyethylene glycol.
• Component (d) is used in an amount of from 10 to 40% by weight based on the total weight of the granular product. If the amount is less than 10% by weight, granulation is difficult. If it exceeds 40% by weight, the resulting granules has reduced solubility.
• the anti-foaming agent granular product comprising components (a) to (d) according to the present invention does not undergo oozing of silicone while exhibiting satisfactory solubility.
• the anti-foaming agent granular product is compounded into a detergent.
• phosphorus-free detergents zeolite-compounded detergents
• the silicone-containing anti-foaming agent granular product are added to phosphorus-free detergents, the granules are coated with water-insoluble zeolite during storage, resulting in reduction in solubility of the granules.
• the granules further contain an anionic surface active agent or a nonionic surface active agent having a melting point or softening point of less than 40°C as component (e).
• Suitable anionic surface active agents as component (e) include sulfonate and sulfate type anionic surface active agents, such as straight chain alkylbenzene­sulfonates, alkylsulfates, polyoxyethylene alkyl ether sulfates, ⁇ -olefinsulfonates, and alkanesulfonates (the salts include sodium salts, potassium salts and the like).
• suitable nonionic surface active agents as component (e) include polyoxyethylene alkyl or alkylphenyl ethers having a melting point or softening point of less than 40°C.
• component (e) is used in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, and more preferably from 0.5 to 5% by weight, based on the total weight of the granular product. If the amount is less than 0.1% by weight, no improvement on solubility can be obtained. If it exceeds 20% by wight, granulation becomes difficult. From the standpoint of granulation properties, anionic surface active agents are preferred as component (e). In using nonionic surface active agents, those having a melting point or softening point of 20°C or higher are preferred from the standpoint of granulation properties.
• the density of the anti-foaming agent granular product according to the present invention is preferably from 0.45 to 0.65 g/cc.
• the anti-foaming agent granular product according to the present invention is desirably produced by a process comprising:
• component (e) i.e., an anionic surface active agent or a nonionic surface active agent having a softening point of less than 40°C is used, it is mixed with the above-­described homogeneous mixture obtained in the step (1) or admixed in the step (2).
• anti-caking agents e.g., silica
• additives such as dyestuffs
• Granulation is preferably performed so that the resulting granules have an average particle size of from 100 to 1,500 ⁇ m, preferably from 200 to 1,300 ⁇ m, and more preferably from 300 to 1,000 ⁇ m. It is also preferable that the resulting granules contain not more than 5% by weight, based on the total weight of the granular product, of particles smaller than 100 ⁇ m and/or not more than 5% by weight, based on the total weight of the granular product, of particles greater than 1,500 ⁇ m.
• the thus obtained anti-foaming agent granular product of the present invention is mixed into a powdered detergent in a proportion of from 0.1 to 5% by weight based on the total weight of the detergent.
• the powdered detergent is not particularly limited, but it is a detergent containing an anionic surface active agent as a main detergent base that is required to be combined with an anti-foaming agent.
• Such a detergent generally comprises from 10 to 60% by weight, based on the total weight of the detergent, of anionic surface active agents, such as straight chain alkylbenzenesulfonates, alkylsulfates, polyoxyethylene alkyl ether sulfates, ⁇ -­olefinsulfonates, and higher fatty acid salts (the salts include sodium salts and potassium salts); from 30 to 80% by weight, based on the total weight of the detergent, of builders, such as carbonates, silicates, sulfates, phosphates, and zeolite; up to 30% by weight, based on the total weight of the detergent, of nonionic surface active agents (e.g., polyoxyethylene alkyl ethers), cationic surface active agents, amphoteric surface active agents, or bleaching agents, such as percarbonates and perborates; and from 2 to 8% by weight, based on the total weight of the detergent, of other components, such as anti-redeposition agents (e.g., carb
• the anti-foaming agent granular product of the present invention is also useful for detergents containing a nonionic surface active agent as a main detergent base since they are foamy under laundry conditions in European countries.
• the anti-foaming agent granular product of the invention is further useful as well for other detergents required to have anti-foaming properties, such as detergents for dish washing.
• the anti-foaming agent granular product according to the present invention when compounded into a powdered detergent, does not cause oozing of silicone during storage and hence, undergoes no reduction in anti-foaming effect. Moreover, since the anti-foaming agent granular product employs water-soluble starch as a carrier for a silicone anti-foaming agent, it exhibits satisfactory solubility in water and leaves no insoluble matter on laundry.
• the anti-foaming agent 20 g of silicone (compound type, "FS Anti-Foam”, trade name, produced by Dow Corning Co.) were mixed with 100 g of maltodextrin (enzyme-modified dextrin, produced by Niezen Kagaku Co., Ltd.) to prepare a homogeneous mixture.
• the resulting homogeneous mixture, polyethylene glycol, and neutral anhydrous sodium sulfate were mixed at a ratio shown below at a temperature of from 70 to 80°C and granulated by means of an extrusion granulator ("Model EXKS-­ 1", trade name, manufactured by Fuji Powdal Co., Ltd.) to obtain granules.
• Composition of Anti-Foaming Granules Homogeneous mixture 50% Polyethylene glycol (PEG-6000, melting point: 58°C) 25% Neutral anhydrous sodium sulfate 25%
• Particle Size Distribution Average particle size: 800 ⁇ m Particles having a particle size of 1000 ⁇ m or greater: 5% Particles having a particle size of 250 ⁇ m or smaller: 5%
• the resulting granules had satisfactory water solubility.
• Water solubility was examined by adding 300 mg of the granules to 300 ml of water at 10°C placed in a 500 ml beaker while stirring by means of a stumble bar (length: 5cm) at a rotation rate of about 500 to about 700 rpm. As a result, all the granules were dissolved within 2 minutes.
• a powdered detergent having the following composition and a bulk density of 0.7 g/cm3 was prepared.
• Washing test was conducted using the powdered detergent containing the anti-foaming component under the following conditions. The height of foam was determined after each of first, second and third time washing. Washing test was conducted thrice and the results were expressed in the average value thereof. Washing Conditions: Washing machine: "Ginga” produced by Toshiba Corp.; volume: 2.2 kg Amount of Water: 30 l Amount of Detergent: 25 g Laundry: 600 g of cotton shirts and 400 g of T/C (Tetoron/cotton union yarn) shirts each having been worn for 3 days were washed three times. Washing Time: 7 minutes each
• the powdered detergent containing the anti-foaming component was stored at 5°C, 30°C, or 40°C for 20 days and then subjected to washing test under the same washing conditions as in (1) above (washing was conducted only once). The height of foam was determined after washing. The test was conducted thrice and the results were expressed in the average value thereof.
• Anti-Foaming Component (part) 1) Silicone 2) - 0.5 - - - Homogeneous Mixture 3) - - 0.5 - - - Anti-Foaming Agent Granules 4) - - - 0.5 1 2 Foam Retention (cm): 1st Washing 8 2 2 1-2 0-1 0 2nd Washing 8 2-3 2-3 2 1 0-1 3rd Washing 7-8 3 3 2-3 2 1 Anti-Foaming Effect after storage (cm): stored at 40°C 8 8 6 2 1 0-1 stored at 30°C 8 7 5-6 1-2 0-1 0 stored at 5°C 8 6 5 0 0 0 Note: 1): Per 100 parts of the detergent 2): Silicone compound produced by Dow Corning Co. 3): Maltodextrin.silicone homogeneous mixture prepared in Example 1 4): Granules prepared in Example 1
• the anti-foaming agent 20 g of silicone (compound type, "FS Anti-Foam”, trade name, produced by Dow Corning Co.) were mixed with 100 g of maltodextrin (enzyme-modified dextrin, produced by Niezen Kagaku Co., Ltd.) to prepare a homogeneous mixture. To the mixture was added 10 g of an alkyl ether sulfate ("Emal 10 Powder", trade name, an anionic surface active agent produced by Kao Corp.) to obtain a mixture.
• an alkyl ether sulfate "Emal 10 Powder", trade name, an anionic surface active agent produced by Kao Corp.
• Particle Size Distribution Average particle size: 800 ⁇ m Particles having a particle size of 1000 ⁇ m or greater: 5% Particles having a particle size of 250 ⁇ m or smaller: 5%
• a powdered detergent having the following composition and a bulk density of 0.7 g/cm3 was prepared.
• the powdered detergent containing the anti-foaming component was stored at 5°C, 30°C, or 40°C for 20 days and then subjected to anti-foaming effect after storage as in (2) above under the same washing conditions as in (1) above (washing was conducted only once). At this time, solubility of granular anti-foaming component after storage was examined by fixing an open mesh bag for collecting flocks (product of Leck Co., Ltd.) was to the washing machine tub. Any insoluble matter collected in the bag was observed and rated as follows.
• the anti-foaming agent 35 g of silicone (compound type, "FS Anti-Foam”, trade name, produced by Dow Corning Co.) were mixed with 100 g of maltodextrin (enzyme-modified dextrin, produced by Niezen Kagaku Co., Ltd.) to prepare a homogeneous mixture. To the mixture was added 3 g of an alkyl ether sulfate ("Emal 10 Powder", trade name, an anionic surface active agent produced by Kao Corp.) to obtain a mixture.
• an alkyl ether sulfate "Emal 10 Powder", trade name, an anionic surface active agent produced by Kao Corp.
• the resulting mixture, polyethylene glycol (product of Sanyo Chemical Industries, Ltd.), and neutral anhydrous sodium sulfate (product of Shikoku Kasei Co., Ltd.) were mixed at a ratio shown below at a temperature of from 70 to 80°C and granulated by means of an extrusion granulator ("Model EXKS-­1", trade name, manufactured by Fuji Powdal Co., Ltd.) to obtain granules.
• Composition of Anti-Foaming Agent Granular Product Homogeneous mixture/anionic surface active agent mixture 75% Polyethylene glycol (PEG-6000, melting point: 58°C) 22% Neutral anhydrous sodium sulfate 3%
• Particle Size Distribution Average particle size: 800 ⁇ m Particles having a particle size of 1000 ⁇ m or greater: 5% Particles having a particle size of 250 ⁇ m or smaller: 5%
• Example 4 A hundred parts of the powdered detergent obtained in Example 4 were mixed with 1.5 part of the anti-foaming agent granules obtained in Example 5, and the resulting detergent was evaluated for retention of foam, anti-foaming effect after storage, and solubility of the anti-foaming agent after storage in the same manner as in Example 4.

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• 1990
  • 1990-06-20 JP JP2163886A patent/JPH0665365B2/ja not_active Expired - Fee Related
  • 1990-08-18 MY MYPI90001391A patent/MY107392A/en unknown
  • 1990-08-22 DE DE69024134T patent/DE69024134T2/de not_active Expired - Fee Related
  • 1990-08-22 EP EP90116082A patent/EP0414221B1/de not_active Expired - Lifetime
• 1996
  • 1996-06-27 HK HK108296A patent/HK108296A/xx not_active IP Right Cessation

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