EP0106634B1 - Bodies containing bleach activators - Google Patents
Bodies containing bleach activators Download PDFInfo
- Publication number
- EP0106634B1 EP0106634B1 EP19830306046 EP83306046A EP0106634B1 EP 0106634 B1 EP0106634 B1 EP 0106634B1 EP 19830306046 EP19830306046 EP 19830306046 EP 83306046 A EP83306046 A EP 83306046A EP 0106634 B1 EP0106634 B1 EP 0106634B1
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- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- bleach activator
- water
- bleach
- bodies
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
Definitions
- the present invention relates to bodies containing bleach activators.
- this invention relates to bodies containing bleach activators. which comprise specific bleach activators and binder material.
- said bleach activators have excellent storage stability and, yet, maintain excellent dispersibility in wash water.
- peroxygen bleaches provide a desirable level of bleaching performance, but that they are also extremely temperature dependent.
- Such bleaches are essentially only practicable and/or effective in bleaching solutions ; i. e., a bleach and water mixture, wherein the solution temperature is above about 60 °C.
- bleach solution temperatures of about 60 °C peroxygen bleaches are only partially effective, due to their low level of reactivity. Therefore, in order to obtain a desirable level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. As the bleach solution temperature is lowered below 60 °C, even higher levels of peroxygen bleach must be added to the system in order to obtain a desirable level of bleaching performance.
- peroxygen bleaches are commonly used as a detergent adjuvant in textile wash processes that utilize an automatic household washing machine at wash water temperatures below 60 °C. Such wash temperatures are utilized because of textile care and energy considerations.
- bleach activators that render peroxygen bleaches effective at bleach solution temperatures below 60 °C. Numerous substances have been disclosed in the art as effective bleach activators.
- Carboxylic acid ester bleach activators are known.
- U.K. Patent 864,798, Hampson et al (April 6, 1961), discloses bleaching compositions comprising an inorganic persalt and-an organic ester of an aliphatic carboxylic acid wherein the size of the carboxylic acid ester particles are such that at least 70 % of them are retained on a 60 mesh British Standard sieve. It is stated that such bleaching compositions are stable during storage. It is preferred that the ester be derived from an aliphatic carboxylic acid having not more than 10, preferably less than 8 carbon atoms.
- U.S. Patent 4,009,113 Green et al, February 22, 1977 discloses granular compositions comprising from about 40 % to about 80 % of a bleach activator and an inert carrier material such as a long chain fatty acids or esters wherein said precursor is substantially evenly distributed with said precursor compound to form a composite particle.
- the particle has an outer protective layer which can consist of, for example, polyvinyl alcohol. It is stated that such compositions have both good storage stability and dispersibility in the wash water.
- U.S. Patent 4,399,049 Gray et al discloses a detergent additive composition comprising from about about 75 % to about 95 % of a particulate infusible solid having a particle size distribution such that at least about 50 % thereof passes a 250 micrometer screen and comprising storage sensitive detergent additive materials, and from about 5 % to about 25 % of ethoxylated nonionic surfactants melting in the range from about 20 °C to about 60 °C wherein said composition is prepared via a radial extrusion process. It is stated that such compositions have improved storage stability together within excellent release and dispersibility characteristics in wash water.
- the present invention comprises a body containing bleach activators comprising :
- This invention relates to a body containing bleach activators which comprise specific bleach activators and binder material, both of which are defined hereinafter.
- the bleach activators in the body have excellent storage stability and, yet, readily disperse in the wash water. Also when the bodies. are utilized as disclosed in the Applicants pending European patent Application No. 83200938.5 (EP-A-0098021). A superior level of bleaching performance on textiles is obtained.
- the bleach activator and binder material are substantially evenly distributed throughout the body and that the body has the proper density.
- Experimental evidence indicates that compacting the bleach activator particles to form a body with a density within the invention and then coating it with the binder material does not provide the desired level of storage stability. Only when the bleach activator and binder material are substantially evenly distributed throughout the body is the storage stability excellent.
- the density of the body be above 1.06 grams/cubic centimeter (g/cc), preferably above 1.08 g/cc, most preferably from 1.10 g/cc to 1.30 g/cc.
- the body must also be essentially free of moisture. The presence of excess free moisture will result in very poor storage stability because of the bleach activator's susceptibility to hydrolysis. Thus, the body must contain less than 3 % water and preferably less than 1.5 % water.
- Control of the particle size of the body is also of some importance for securing optimum storage stability and dispersibility in the wash water. It is preferred that the bodies have a particle size distribution from 0.05 mm to 2.5 millimeters wherein no more than 5 % of the bodies are greater than 2 millimeters and more preferably from 0.30 mm to 1.5 millimeters.
- the body can be made by essentially any apparatus that is suitable to substantially evenly distribute the bleach activator and binder material throughout the body and compact the body in order to obtain the required density.
- powder blenders can be utilized to mix the bleach activator and binder material and then the mixture can be passed through a radial or axial extruder or a compaction press to form the body. Radial or axial extruders are preferred because it is believed that they produce a body in which the bleach activator has both superior storage stability and dispersibility in the wash water.
- the binder material should be in fluid form. This can be accomplished by either heating the mixture until the binder material melts or, -especially with binder materials that decompose rather than melt upon heating, forming an aqueous solution.
- the bleach activators that can be utilized in the bodies within the invention have the general formula : wherein R is an alkyl group containing form 5 to 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms and L is a leaving group that contains an anionic moiety, the conjugate acid of which has a pK, in the range of from 6 to 13.
- L can be essentially any suitable leaving group that contains an anionic moiety.
- a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion.
- a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion yielded by the peroxygen bleach which is believed to be essential in order to obtain a superior level of bleaching performance.
- Leaving groups that exhibit such behavior are those in which their conjugate acid has a pK a in the range of from 6 to 13, preferably from 7 to 11 and most preferably from about 8 to about 11.
- the leaving group in order for the body to have the desired level of dispersibility in the wash water it is essential that the leaving group contain an anionic moiety.
- a leaving group that does not contain an anionic moiety does not provide the desired level of dispersibility in the wash water.
- suitable anionic moieties are -S0 3 M + , -COO-M+ and -SO 4 -M + wherein M is a compatible cation.
- Preferred bleach activators are those of the above general formula wherein R is as defined in the general formula and L is selected from wherein R is as defined above, R 2 is an alkyl chain containing from 1 to 8 carbon atoms, R 3 is H or R 2 , and Y is selected from -SO 3 -M + , -C00-M+ and -S04-M+ and most preferably -SO 3 -M + and -COO-M + , M is selected from alkali metals, ammonium and substituted ammonium cations, with sodium and potassium being most preferred.
- Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula and R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms.
- More preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from 5 to 9 and preferably from 7 to 9 carbon atoms and L is selected from wherein R, R 2 , R 3 and Y are as defined above.
- Particularly preferred bleach activators are those of the above general formula wherein R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from 6 to 10 carbon atoms and L is selected from wherein R 2 is as defined above and Y is -SO 3 -M + or -COO-M + wherein M is as defined above.
- Especially preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from 5 to 9 and preferably from about 7 to about 9 carbon atoms and L is selected from wherein R 2 is as defined and Y is -SO 3 -M + or -COO-M + wherein M is as defined above.
- the most preferred bleach activators have the formula : wherein R is a linear alkyl chain containing from 5 to 9 and preferably from 7 to 9 carbon atoms and M is sodium or potassium.
- the level of bleach activator within the bodies of the invention is from 50 % to 98 % and preferably from 85 % to 96 %. It is also preferred that the bleach activator particle size distribution is from 5 ⁇ m to 2.5 millimeters wherein no more than 2 % of the particles are greater than 2 millimeters and more preferably from 25 to 150 ⁇ m.
- the materials that can be utilized as binders are nonionic surfactants, polyethylene glycols, fatty acids, anionic surfactants, film forming polymers and mixtures thereof. It is believed that such binder materials are not reactive with the bleach activator and, if in a detergent composition, not reactive with the components of the detergent composition upon storage. Also, they have low hygroscopicity upon storage and, yet, are soluble and, therefore, dispersible in the wash water. However, it is essential that such binder materials do not melt below about 40 °C. Otherwise, the binder is likely to melt upon storage because often the storage temperature is as high as 40 °C. Naturally, the melting of the binder material results in the bleach activator being quite unstable. It should be noted that some of the binder materials within the invention will decompose rather than melt upon the application of heat energy. However, the temperature at which such binder materials decompose is well beyond any temperature at which the bodies will be stored.
- Nonionic surfactants are the least preferred binder materials because it is believed that they have an inimical effect on cleaning performance on textiles when the bodies are utilized as disclosed in the Applicants pending European patent Application No. 83 200 938.5 (EP-A-0 098 021
- nonionic surfactants that can be utilized as a binder material are the condensation product of primary of secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 35 to 100 moles, preferably 40 to about 80 moles of ethylene oxide per mole of alcohol.
- the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 35 and 100, desirably between 40 and 80 moles of ethylene oxide per mole of aliphatic alcohol.
- the preferred nonionic surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.
- nonionic surfactants are the polyethylene oxide condensates of alkyl phenol, e. g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 35 to 100, preferably 40 to 80 moles of ethylene oxide per mole of alkyl phenol.
- the alkyl substituent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene and nonene.
- nonionic surfantants suitable for use herein are the compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
- the molecular weight of the hydrophobic portion generally falls in the range of 1 500 to 1 800.
- Such synthetic nonionic detergents are available on the market under the Trade Name of « Pluronic » supplied by Wyandotte Chemicals Corporation.
- Suitable polyethylene glycols which are homopolymers of ethylene oxide having the general formula have an average molecular weight of from 2000 to 15 000, preferably from 3 000 to 10000 and most preferably from 4 000 to 8 000.
- the fatty acids that are suitable for use herein are higher fatty acids containing from 8 to 24 carbon atoms and preferably from 12 to 18 carbon atoms. It has also been observed that mixtures of fatty acids and nonionic binder materials, e. g., polyethylene glycols or nonionic surfactants, provide the bleach activator with particularly good storage stability and dispersibility in the wash water. It is believed that fatty acids reduce the hygroscopicity of the nonionic binder materials and that the nonionic binder materials improve the dispersibility of the fatty acids. I
- Suitable anionic surfactants are the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term « afkyl » is the alkyl portion of acyl groups).
- Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil ; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e. g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
- the preferred anionic surfactants are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS.
- anionic surfactants herein are the water-soluble salts of the higher fatty acids, i. e., « soaps •, are useful anionic surfactants in the compositions herein.
- anionic surfactants for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil ; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates ; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms ; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group ; water-soluble salts of 2-acyloxyafkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety ; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Suitable film forming polymers are the polymers derived from the monomers such as vinyl chloride, vinyl alcohol, furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid.
- Preferred polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the copolymers contain at least 50 %, and preferably at least 80 %, by weight of units derived from the acid.
- the particularly preferred polymer is sodium polyacrylate.
- Other specific preferred polymers are the homopolymers and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene and vinyl methyl ether. These polymers are commercially available under the trade names VersicolS and Gantrez®.
- film-forming polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate and hydroxypropylcellulose sulfate.
- the level of binder material within the bodies within the invention is from 2 % to 50 % and preferably from 4 % to 15 %.
- the bodies of the present invention can also contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936.537, Baskerville et al. so long as they are inert with respect to the bleach activator and binder material.
- Such components include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
- the following granular detergent composition was prepared :
- 600 parts of the bleach activator powdered sodium linear octanoyloxybenzene sulfonate which passes through a 0.149 mm screen and 180 parts of a binder material consisting of 50 % water, 32 % C 13 linear alkylbenzene sulfonate and 18 % sodium sulfate were utilized in a fluidized bed to produce bodies containing the bleach activator of particle sizes that passed through a 0.595 mm screen onto a 0.21 mm screen. The bodies- were then dried to remove all the water. The density of the bodies was then determined via mercury intrusion.
- a composition consisting of 86 % of the above granular detergent composition, 6 % sodium perborate monohydrate and 8 % of the bodies was prepared.
- the composition was placed in a glass jar and stored for four weeks wherein the storage room temperature ranged from 27 °C to 32 °C and room humidity ranged from 60 % to 80 %.
- the bodies were prepared by placing 50 parts of the above bleach activator in a mixer and then spraying them with 4 parts water. The bodies were then dried. The size of the bodies was such that they passed through a 1.68 mm screen onto a 0.42 mm screen. The bodies then were coated with a C 13 linear alkylbenzene sulfonate paste binder material.
- the bodies prepared via the fluid bed have the binder paste substantially evenly distributed throughout the bodies containing the bleach activator, but have a density outside the invention provided poor storage stability for the bleach activator.
- the bodies prepared via the mixer have a density within the invention, but do not have the binder material substantially evenly distributed throughout the bodies containing the bleach activator did not provide the desired level of storage stability of the bleach activator. Only the bodies prepared via extrusion, which have both a density within the invention and the binder material substantially evenly distributed throughout the body, provided excellent storage stability for the bleach activator
- Example II A sample of the bodies prepared via radial extrusion in Example I were admixed with the granular detergent composition of Example 1. A quantity of sodium perborate monohydrate corresponding to a molar ratio of sodium perborate monohydrate to bleach activator of 3.3 was added to the system. The entire system was then placed in a beaker containing 37 °C water.
- the amount of available oxygen from percarboxylic acid was measured as in Example 1, 3 minutes, 5 minutes and then 15 minutes after the system was placed in the beaker. Then the percent conversion of sodium linear octanoyloxybenzene sulfonate to percarboxylic acid was calculated for each time period.
- Bleach Activator System I which is within the invention, produced higher percentage conversion of activator to percarboxylic acid in a shorter period of time than Bleach Activator System III, which is outside -the invention because it did not contain a bleach activator within the invention. It should be noted that though Bleach Activator System III achieved 100 % conversion after 15 minutes, that this level of dispersibility would not be sufficient in a textile wash process because it would not allow enough time for the bleaching process to occur.
- Ten sets of four 12.5 x 12.5 cm swatches consisting of standard textiles and five sets of four terry cloth towels were preconditioned by adding artificial body soils to them so as to simulate the condition of household laundry that has been subjected to routine wear. Each set of four swatches was then stained with a different bleachable stain. The swatches were then cut in half to produce 20 sets of half swatches with half of the stain being on each half of the swatch. One terry cloth towel from each set of terry cloth towels was then soiled with a mixture of artificial body soil and vacuum cleaner soil.
- the laundry load in the first mini-wash system was washed with a quantity of the detergent composition of Example I that corresponds to 1 500 ppm in the wash water which is typical of conventional automatic wash processes.
- the mini-wash system with such a load simulates a conventional automatic wash process.
- the wash water temperature was 37 °C and the rinse water temperature was 22 °C and both contained 120 ppm Ca ++ water hardness.
- Each of the swatches was then comparison graded with its original other half to determine relative stain removal.
- a grading scale of -4 to 4 was used, with -4 indicating much less stain removal, 0 indicating no difference and 4 indicating much more stain removal.
- the average of the grades for each stain of each mini-wash system was calculated.
- Bleach Activator System II which has bodies containing a bleach activator within the invention, not only provided significantly better bleaching performance than Bleach Activator System IV, which has bodies containing bleach activators outside the invention, but significantly better bleaching performance than Bleach Activator System V, which contains a powdered bleaching system.
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Description
- The present invention relates to bodies containing bleach activators. In particular, this invention relates to bodies containing bleach activators. which comprise specific bleach activators and binder material. In such bodies said bleach activators have excellent storage stability and, yet, maintain excellent dispersibility in wash water.
- It has long been known that peroxygen bleaches provide a desirable level of bleaching performance, but that they are also extremely temperature dependent. Such bleaches are essentially only practicable and/or effective in bleaching solutions ; i. e., a bleach and water mixture, wherein the solution temperature is above about 60 °C. At bleach solution temperatures of about 60 °C peroxygen bleaches are only partially effective, due to their low level of reactivity. Therefore, in order to obtain a desirable level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. As the bleach solution temperature is lowered below 60 °C, even higher levels of peroxygen bleach must be added to the system in order to obtain a desirable level of bleaching performance. The temperature dependence of peroxygen bleaches is significant because such bleaches are commonly used as a detergent adjuvant in textile wash processes that utilize an automatic household washing machine at wash water temperatures below 60 °C. Such wash temperatures are utilized because of textile care and energy considerations. As a consequence of such wash processes, there thas been much industrial research to develop substances, generally referred to as bleach activators, that render peroxygen bleaches effective at bleach solution temperatures below 60 °C. Numerous substances have been disclosed in the art as effective bleach activators.
- Carboxylic acid ester bleach activators are known. U.K. Patent 864,798, Hampson et al (April 6, 1961), discloses bleaching compositions comprising an inorganic persalt and-an organic ester of an aliphatic carboxylic acid wherein the size of the carboxylic acid ester particles are such that at least 70 % of them are retained on a 60 mesh British Standard sieve. It is stated that such bleaching compositions are stable during storage. It is preferred that the ester be derived from an aliphatic carboxylic acid having not more than 10, preferably less than 8 carbon atoms.
- U.K. Patent 836,988, Davies et al (June 9, 1960), discloses bleaching compositions containing hydrogen peroxide or inorganic persalt and organic carboxylic esters. A test is described to define the esters within the invention. It is stated that such esters provide improved bleaching at temperatures from 50 °C to 60 °C relative to that obtained with the persalt alone.
- It is also known that peroxygen bleaches in combination with bleach activators that are believed to exhibit surface activity provide particularly effective bleaching performance. U.S. Patent 4,283.301, Diehl (August 11, 1981), discloses bleaching compositions comprising a peroxygen bleach and a bleach activator of the general formula :
- It has also been long known that the function of a bleach activator can be significantly impaired during storage by interaction with the peroxygen bleach and/or moisture and, if the bleach activator is part of a detergent composition, interaction with other components of the detergent composition. Therefore, for the bleach activator to retain its efficacy, it must be protected from its environment during storage. However, any method of protecting the bleach activator from its environment must not substantially inhibit its ability to disperse in the wash water.
- U.S. Patent 4,009,113 Green et al, February 22, 1977, discloses granular compositions comprising from about 40 % to about 80 % of a bleach activator and an inert carrier material such as a long chain fatty acids or esters wherein said precursor is substantially evenly distributed with said precursor compound to form a composite particle. The particle has an outer protective layer which can consist of, for example, polyvinyl alcohol. It is stated that such compositions have both good storage stability and dispersibility in the wash water.
- U.S. Patent 4,399,049 Gray et al (August 16 1983) discloses a detergent additive composition comprising from about about 75 % to about 95 % of a particulate infusible solid having a particle size distribution such that at least about 50 % thereof passes a 250 micrometer screen and comprising storage sensitive detergent additive materials, and from about 5 % to about 25 % of ethoxylated nonionic surfactants melting in the range from about 20 °C to about 60 °C wherein said composition is prepared via a radial extrusion process. It is stated that such compositions have improved storage stability together within excellent release and dispersibility characteristics in wash water.
- The present invention comprises a body containing bleach activators comprising :
- (a) from 50 % to 98 % of a bleach activator having the general formula :
- (b) from 2 % to 50 % of a binder material selected from the group consisting of nonionic surfactants, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereof wherein said binder does not melt below 40 °C ;
- This invention relates to a body containing bleach activators which comprise specific bleach activators and binder material, both of which are defined hereinafter. The bleach activators in the body have excellent storage stability and, yet, readily disperse in the wash water. Also when the bodies. are utilized as disclosed in the Applicants pending European patent Application No. 83200938.5 (EP-A-0098021). A superior level of bleaching performance on textiles is obtained.
- It is essential that the bleach activator and binder material are substantially evenly distributed throughout the body and that the body has the proper density. Experimental evidence indicates that compacting the bleach activator particles to form a body with a density within the invention and then coating it with the binder material does not provide the desired level of storage stability. Only when the bleach activator and binder material are substantially evenly distributed throughout the body is the storage stability excellent. However, it is also essential that the density of the body be above 1.06 grams/cubic centimeter (g/cc), preferably above 1.08 g/cc, most preferably from 1.10 g/cc to 1.30 g/cc. Experimental evidence also indicates that though the bleach activator and binder material are substantially evenly distributed throughout the body, densities below 1.06 g/cc do not provide the desired level of storage stability. It should be noted that the specific densities were measured by a mercury displacement method in which air is removed from a vessel containing a weighed sample of the particles (bodies), mercury is introduced, and the pressure increased in increments. The rate of volume decrease (or density increase) is typically one value when interparticulate spaces are being filled, which occurs first, and a different value when the'voids in the particle are being filled. The inflection point on the volume-pressure curve is taken as indicating the specific density of the particles.
- The body must also be essentially free of moisture. The presence of excess free moisture will result in very poor storage stability because of the bleach activator's susceptibility to hydrolysis. Thus, the body must contain less than 3 % water and preferably less than 1.5 % water.
- Control of the particle size of the body is also of some importance for securing optimum storage stability and dispersibility in the wash water. It is preferred that the bodies have a particle size distribution from 0.05 mm to 2.5 millimeters wherein no more than 5 % of the bodies are greater than 2 millimeters and more preferably from 0.30 mm to 1.5 millimeters.
- The body can be made by essentially any apparatus that is suitable to substantially evenly distribute the bleach activator and binder material throughout the body and compact the body in order to obtain the required density. For example, powder blenders can be utilized to mix the bleach activator and binder material and then the mixture can be passed through a radial or axial extruder or a compaction press to form the body. Radial or axial extruders are preferred because it is believed that they produce a body in which the bleach activator has both superior storage stability and dispersibility in the wash water. It should be noted that when the bleach activator and binder material are mixed, the binder material should be in fluid form. This can be accomplished by either heating the mixture until the binder material melts or, -especially with binder materials that decompose rather than melt upon heating, forming an aqueous solution.
- The following is a detailed description of the essential components of the body containing bleach activators within the invention. All percentages, parts and ratios are by weight unless otherwise indicated.
- The bleach activators that can be utilized in the bodies within the invention have the general formula :
- L can be essentially any suitable leaving group that contains an anionic moiety. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. Generally, for a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion yielded by the peroxygen bleach which is believed to be essential in order to obtain a superior level of bleaching performance. Leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from 6 to 13, preferably from 7 to 11 and most preferably from about 8 to about 11. Also, in order for the body to have the desired level of dispersibility in the wash water it is essential that the leaving group contain an anionic moiety. A leaving group that does not contain an anionic moiety does not provide the desired level of dispersibility in the wash water. Nonlimiting examples of suitable anionic moieties are -S03 M+, -COO-M+ and -SO4-M+ wherein M is a compatible cation.
- Preferred bleach activators are those of the above general formula wherein R is as defined in the general formula and L is selected from
- Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula and R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms.
- Even more preferred are bleach activators of the above general formula wherein L is as defined in the general formula and R is a linear alkyl chain containing from 5 to 9 and preferably from 7 to 9 carbon atoms.
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- Particularly preferred bleach activators are those of the above general formula wherein R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from 6 to 10 carbon atoms and L is selected from
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- The level of bleach activator within the bodies of the invention is from 50 % to 98 % and preferably from 85 % to 96 %. It is also preferred that the bleach activator particle size distribution is from 5 µm to 2.5 millimeters wherein no more than 2 % of the particles are greater than 2 millimeters and more preferably from 25 to 150 µm.
- The materials that can be utilized as binders are nonionic surfactants, polyethylene glycols, fatty acids, anionic surfactants, film forming polymers and mixtures thereof. It is believed that such binder materials are not reactive with the bleach activator and, if in a detergent composition, not reactive with the components of the detergent composition upon storage. Also, they have low hygroscopicity upon storage and, yet, are soluble and, therefore, dispersible in the wash water. However, it is essential that such binder materials do not melt below about 40 °C. Otherwise, the binder is likely to melt upon storage because often the storage temperature is as high as 40 °C. Naturally, the melting of the binder material results in the bleach activator being quite unstable. It should be noted that some of the binder materials within the invention will decompose rather than melt upon the application of heat energy. However, the temperature at which such binder materials decompose is well beyond any temperature at which the bodies will be stored.
- Nonionic surfactants are the least preferred binder materials because it is believed that they have an inimical effect on cleaning performance on textiles when the bodies are utilized as disclosed in the Applicants pending European patent Application No. 83 200 938.5 (EP-A-0 098 021
- Examples of nonionic surfactants that can be utilized as a binder material are the condensation product of primary of secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 35 to 100 moles, preferably 40 to about 80 moles of ethylene oxide per mole of alcohol. Preferably, the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 35 and 100, desirably between 40 and 80 moles of ethylene oxide per mole of aliphatic alcohol. The preferred nonionic surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e. g., myristyl, cetyl, stearyl alcohols), or partly branched such as the Dobanols and Neodols which have about 25 % 2-methyl branching (Dobanol® and Neodol® being Trade Names of Shell or Synperonics, which are understood to have about 50 % 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50 % branched chain structure sold under the Trade Name Lial@ by Liquichimica.
- Other suitable nonionic surfactants are the polyethylene oxide condensates of alkyl phenol, e. g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 35 to 100, preferably 40 to 80 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene and nonene.
- Still further nonionic surfantants suitable for use herein are the compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of 1 500 to 1 800. Such synthetic nonionic detergents are available on the market under the Trade Name of « Pluronic » supplied by Wyandotte Chemicals Corporation.
-
- The fatty acids that are suitable for use herein are higher fatty acids containing from 8 to 24 carbon atoms and preferably from 12 to 18 carbon atoms. It has also been observed that mixtures of fatty acids and nonionic binder materials, e. g., polyethylene glycols or nonionic surfactants, provide the bleach activator with particularly good storage stability and dispersibility in the wash water. It is believed that fatty acids reduce the hygroscopicity of the nonionic binder materials and that the nonionic binder materials improve the dispersibility of the fatty acids. I
- Suitable anionic surfactants are the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term « afkyl » is the alkyl portion of acyl groups). Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil ; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e. g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. The preferred anionic surfactants are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11-13LAS.
- - Other anionic surfactants herein are the water-soluble salts of the higher fatty acids, i. e., « soaps •, are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Other anionic surfactants for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil ; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates ; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms ; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group ; water-soluble salts of 2-acyloxyafkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety ; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Suitable film forming polymers are the polymers derived from the monomers such as vinyl chloride, vinyl alcohol, furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid.
- Preferred polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the copolymers contain at least 50 %, and preferably at least 80 %, by weight of units derived from the acid. The particularly preferred polymer is sodium polyacrylate. Other specific preferred polymers are the homopolymers and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene and vinyl methyl ether. These polymers are commercially available under the trade names VersicolS and Gantrez®.
- Other film-forming polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate and hydroxypropylcellulose sulfate.
- Surprisingly, very small levels of binder material within the body are required. The level of binder material within the bodies within the invention is from 2 % to 50 % and preferably from 4 % to 15 %.
- The bodies of the present invention can also contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936.537, Baskerville et al. so long as they are inert with respect to the bleach activator and binder material. Such components include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
- The following examples are given to illustrate the parameters of and compositions within the invention. All percentages, parts and ratios are by weight unless otherwise indicated.
-
- 600 parts of the bleach activator powdered sodium linear octanoyloxybenzene sulfonate which passes through a 0.149 mm screen and 180 parts of a binder material consisting of 50 % water, 32 % C13 linear alkylbenzene sulfonate and 18 % sodium sulfate were utilized in a fluidized bed to produce bodies containing the bleach activator of particle sizes that passed through a 0.595 mm screen onto a 0.21 mm screen. The bodies- were then dried to remove all the water. The density of the bodies was then determined via mercury intrusion.
- A composition consisting of 86 % of the above granular detergent composition, 6 % sodium perborate monohydrate and 8 % of the bodies was prepared. The composition was placed in a glass jar and stored for four weeks wherein the storage room temperature ranged from 27 °C to 32 °C and room humidity ranged from 60 % to 80 %.
- 10 Grams of the composition was then added to a beaker containing 500 cc. of 37 °C water. The water contained 120 ppm Ca""" water hardness. The water was continuously stirred for about 10 minutes and then the amount of available oxygen from percarboxylic acid was measured utilizing an iodometric titration procedure. This measurement was compared to the maximum theoretical amount of available oxygen from percarboxylic acid to determine the percent of the retained reactivity of the bleach activator.
- The entire above procedure was repeated but with bodies consisting of 100 parts of the above bleach activator and 18 parts of the above binder material prepared via radial extrusion. The noodle like extrudates were then dried and granulated. The size of the bodies was such that they passed through a 1.68 mm screen onto a 0.42 mm screen.
- Once again the entire above procedure was repeated, bu the bodies were prepared by placing 50 parts of the above bleach activator in a mixer and then spraying them with 4 parts water. The bodies were then dried. The size of the bodies was such that they passed through a 1.68 mm screen onto a 0.42 mm screen. The bodies then were coated with a C13 linear alkylbenzene sulfonate paste binder material.
-
- The bodies prepared via the fluid bed have the binder paste substantially evenly distributed throughout the bodies containing the bleach activator, but have a density outside the invention provided poor storage stability for the bleach activator. The bodies prepared via the mixer have a density within the invention, but do not have the binder material substantially evenly distributed throughout the bodies containing the bleach activator did not provide the desired level of storage stability of the bleach activator. Only the bodies prepared via extrusion, which have both a density within the invention and the binder material substantially evenly distributed throughout the body, provided excellent storage stability for the bleach activator
- A sample of the bodies prepared via radial extrusion in Example I were admixed with the granular detergent composition of Example 1. A quantity of sodium perborate monohydrate corresponding to a molar ratio of sodium perborate monohydrate to bleach activator of 3.3 was added to the system. The entire system was then placed in a beaker containing 37 °C water.
- The amount of available oxygen from percarboxylic acid was measured as in Example 1, 3 minutes, 5 minutes and then 15 minutes after the system was placed in the beaker. Then the percent conversion of sodium linear octanoyloxybenzene sulfonate to percarboxylic acid was calculated for each time period.
- The above procedure was repeated with sodium linear octanoyloxybenzene sulfonate powder, te- tracetylethylenediamine (TAED) powder and TAED prepared with the same binder material via radial extrusion as in Example I.
-
- Bleach Activator System I, which is within the invention, produced higher percentage conversion of activator to percarboxylic acid in a shorter period of time than Bleach Activator System III, which is outside -the invention because it did not contain a bleach activator within the invention. It should be noted that though Bleach Activator System III achieved 100 % conversion after 15 minutes, that this level of dispersibility would not be sufficient in a textile wash process because it would not allow enough time for the bleaching process to occur.
- Ten sets of four 12.5 x 12.5 cm swatches consisting of standard textiles and five sets of four terry cloth towels were preconditioned by adding artificial body soils to them so as to simulate the condition of household laundry that has been subjected to routine wear. Each set of four swatches was then stained with a different bleachable stain. The swatches were then cut in half to produce 20 sets of half swatches with half of the stain being on each half of the swatch. One terry cloth towel from each set of terry cloth towels was then soiled with a mixture of artificial body soil and vacuum cleaner soil.
- A laundry load consisting of one of the sets of terry cloth towels and four of the sets of half swatches was placed in each of five mini-wash systems. The four sets of half swatches placed in each mini-wash system were chosen so that no half swatch was placed in the same mini-wash system as its original other half.
- The laundry load in the first mini-wash system was washed with a quantity of the detergent composition of Example I that corresponds to 1 500 ppm in the wash water which is typical of conventional automatic wash processes. The mini-wash system with such a load simulates a conventional automatic wash process. The wash water temperature was 37 °C and the rinse water temperature was 22 °C and both contained 120 ppm Ca++ water hardness.
- This wash process was carried out in the other four mini-wash systems, but with each mini-wash system also containing one of the four Bleach Activator Systems of Example II and sodium perborate monohydrate wherein the molar ratio of sodium perborate monohydrate to bleach activator was 3.3.
- Each of the swatches was then comparison graded with its original other half to determine relative stain removal. A grading scale of -4 to 4 was used, with -4 indicating much less stain removal, 0 indicating no difference and 4 indicating much more stain removal. The average of the grades for each stain of each mini-wash system was calculated.
- The entire above procedure was repeated. The average of the two determinations of each of the above described averages was calculated. Finally, the average of all such averages for each mini-wash system was calculated. The average for each system was then scaled from 0 to 100, with 0 being the mini-wash system that provided the least stain removal and 100 being the mini-wash system that provided the most stain removal. This number is known as the Bleaching Index.
-
- Bleach Activator System II, which has bodies containing a bleach activator within the invention, not only provided significantly better bleaching performance than Bleach Activator System IV, which has bodies containing bleach activators outside the invention, but significantly better bleaching performance than Bleach Activator System V, which contains a powdered bleaching system.
wherein (a) and (b) are substantially evenly distributed throughout said body, the density of said body is above 1.06 g/cc and said body contains less than 3 % water.
Claims (7)
wherein (a) and (b) are substantially evenly distributed throughout said body, the density of said body is above 1.06 g/cc and body contains less than 3 % water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83306046T ATE20477T1 (en) | 1982-10-08 | 1983-10-05 | COMPOSITIONS CONTAINING BLEACH ACTIVATORS. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43349982A | 1982-10-08 | 1982-10-08 | |
US433499 | 1982-10-08 | ||
US44197882A | 1982-11-15 | 1982-11-15 | |
US441978 | 1995-05-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0106634A1 EP0106634A1 (en) | 1984-04-25 |
EP0106634B1 true EP0106634B1 (en) | 1986-06-18 |
Family
ID=27029874
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830306046 Expired EP0106634B1 (en) | 1982-10-08 | 1983-10-05 | Bodies containing bleach activators |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0106634B1 (en) |
DE (1) | DE3364205D1 (en) |
ES (1) | ES8504242A1 (en) |
Families Citing this family (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2152041B (en) * | 1983-12-22 | 1987-11-11 | Procter & Gamble | X-substituted derivatives of carboxylic acids used as peroxygen bleach activators |
GB8410826D0 (en) * | 1984-04-27 | 1984-06-06 | Unilever Plc | Bleach products |
DE3415880A1 (en) * | 1984-04-28 | 1985-10-31 | Henkel KGaA, 4000 Düsseldorf | WASHING ADDITIVE |
DE3422055A1 (en) * | 1984-06-14 | 1985-12-19 | Henkel KGaA, 4000 Düsseldorf | WASHING ADDITIVE |
GB8422158D0 (en) * | 1984-09-01 | 1984-10-03 | Procter & Gamble Ltd | Bleach compositions |
EP0195663A3 (en) * | 1985-03-20 | 1987-05-13 | The Procter & Gamble Company | Bleaching compositions |
US5112514A (en) * | 1986-11-06 | 1992-05-12 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
US5002691A (en) * | 1986-11-06 | 1991-03-26 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
US4751015A (en) * | 1987-03-17 | 1988-06-14 | Lever Brothers Company | Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions |
US4818426A (en) * | 1987-03-17 | 1989-04-04 | Lever Brothers Company | Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions |
GB8711153D0 (en) * | 1987-05-12 | 1987-06-17 | Warwick International Ltd | Bleach activator compositions |
US5269962A (en) | 1988-10-14 | 1993-12-14 | The Clorox Company | Oxidant composition containing stable bleach activator granules |
US4997590A (en) * | 1988-12-22 | 1991-03-05 | The Procter & Gamble Company | Process of coloring stabilized bleach activator extrudates |
GB8907100D0 (en) * | 1989-03-29 | 1989-05-10 | Unilever Plc | Particulate detergent additive product,preparation and use thereof in detergent compositions |
GB8919006D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Granulated bleach activator particles |
US5078907A (en) * | 1989-11-01 | 1992-01-07 | Lever Brothers Company, Division Of Conopco, Inc. | Unsymmetrical dicarboxylic esters as bleach precursors |
GB8925621D0 (en) * | 1989-11-13 | 1990-01-04 | Unilever Plc | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
US5258132A (en) * | 1989-11-15 | 1993-11-02 | Lever Brothers Company, Division Of Conopco, Inc. | Wax-encapsulated particles |
US5200236A (en) * | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
US5230822A (en) * | 1989-11-15 | 1993-07-27 | Lever Brothers Company, Division Of Conopco, Inc. | Wax-encapsulated particles |
DE4024759A1 (en) * | 1990-08-03 | 1992-02-06 | Henkel Kgaa | BLEACH ACTIVATORS IN GRANULATE FORM |
DE4143016A1 (en) * | 1991-12-24 | 1993-07-01 | Henkel Kgaa | BLEACH ACTIVATORS IN GRANULATE FORM (II) |
US5480575A (en) * | 1992-12-03 | 1996-01-02 | Lever Brothers, Division Of Conopco, Inc. | Adjuncts dissolved in molecular solid solutions |
GB9323634D0 (en) * | 1993-11-16 | 1994-01-05 | Warwick Int Ltd | Bleach activator compositions |
US5688742A (en) * | 1995-08-18 | 1997-11-18 | Rohm And Haas Company | Water based formation of a beaded product |
US5843879A (en) * | 1996-02-06 | 1998-12-01 | Lion Corporation | Bleaching activator granulate |
EP0816483A1 (en) * | 1996-06-27 | 1998-01-07 | The Procter & Gamble Company | Granular bleaching compositions |
WO1998035010A1 (en) * | 1997-02-10 | 1998-08-13 | The Procter & Gamble Company | Particulate bleach additive composition for use in granular detergent compositions |
US5905067A (en) * | 1997-02-10 | 1999-05-18 | Procter & Gamble Company | System for delivering hydrophobic liquid bleach activators |
DE60012072T2 (en) | 1999-04-20 | 2005-07-21 | Kao Corp. | bleach activator |
DK1433839T4 (en) † | 2002-12-24 | 2015-06-15 | Dalli Werke Gmbh & Co Kg | OPTIMIZED CLEANING AND CLEANING SYSTEM FOR IMPROVED BLOW EFFECTS AT LOW TEMPERATURES |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4009113A (en) * | 1971-04-30 | 1977-02-22 | Lever Brothers Company | Protection of materials |
US4367156A (en) * | 1980-07-02 | 1983-01-04 | The Procter & Gamble Company | Bleaching process and compositions |
US4283301A (en) * | 1980-07-02 | 1981-08-11 | The Procter & Gamble Company | Bleaching process and compositions |
-
1983
- 1983-10-05 EP EP19830306046 patent/EP0106634B1/en not_active Expired
- 1983-10-05 DE DE8383306046T patent/DE3364205D1/en not_active Expired
- 1983-10-07 ES ES526333A patent/ES8504242A1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
EP0106634A1 (en) | 1984-04-25 |
DE3364205D1 (en) | 1986-07-24 |
ES526333A0 (en) | 1985-04-01 |
ES8504242A1 (en) | 1985-04-01 |
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