WO1999047633A1 - Composition de detergent contenant un activateur de blanchiment sous forme d'extrudats cylindriques ayant une coulabilite amelioree - Google Patents

Composition de detergent contenant un activateur de blanchiment sous forme d'extrudats cylindriques ayant une coulabilite amelioree Download PDF

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Publication number
WO1999047633A1
WO1999047633A1 PCT/IB1999/000423 IB9900423W WO9947633A1 WO 1999047633 A1 WO1999047633 A1 WO 1999047633A1 IB 9900423 W IB9900423 W IB 9900423W WO 9947633 A1 WO9947633 A1 WO 9947633A1
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WIPO (PCT)
Prior art keywords
microns
extrudate
carbon atoms
bleach
bleach activator
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PCT/IB1999/000423
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English (en)
Inventor
Adrian John Waynforth Angell
Joseph Adam Pauley, Iii
Steven Matthew Gabriel
Donald Ray Brown
James Bert Royston
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR9908925-4A priority Critical patent/BR9908925A/pt
Priority to JP2000536816A priority patent/JP2002506923A/ja
Priority to EP99906389A priority patent/EP1064348A1/fr
Priority to CA002324397A priority patent/CA2324397A1/fr
Publication of WO1999047633A1 publication Critical patent/WO1999047633A1/fr

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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 extrudates which comprise bleach activators said extrudates having increased flowability.
  • These extrudates are useful in detergent compositions containing a peroxygen bleaching compound which require the bleach activator in the form of substantially cylindrically-shaped extrudate having a selected relatively small particle size.
  • the smaller sized bleach activator extrudates unexpectedly remain stable over extended storage periods and reduce product segregation in the detergent box in which they are contained as they more closely mirror the particle size of other conventional detergent ingredients.
  • the increase flowability of the extrudates taken together with the particle size of the extrudates delivers enhanced sanitization effects to the laundered fabrics more consistently.
  • a bleach containing detergent composition which comprises a bleach activator extrudate, said extrudate comprising: a) from about 60% to about 95% by weight, of a bleach activator having the formula:
  • R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK ⁇ in the range of from about 6 to about 13; ii) from about 0.1% to about 40% by weight, of one or more binder materials; and iii) from about 0.5% to about 10% by weight, of a flowability enhancer; wherein said bleach activator extrudate is in the form of a substantially cylindrically-shaped extrudate having a mean extrudate length of from about 500 microns to about 3500 microns and a mean extrudate diameter of from about 450 microns to about 850 microns and provided said extrudate comprises sufficient activator such that the ratio of bleach activator to peroxygen bleaching compound is greater than 1; and c) the balance carriers and other adjunct ingredients.
  • a detergent composition containing a bleach activator particles which have good stability prior to use and acceptable physical properties. It is also an object of the invention to provide a detergent composition containing a bleach activator which does not significantly segregate while stored in the detergent product box. Another object of the invention is to provide such a detergent product which can be used to sanitize fabrics.
  • the detergent or bleaching compositions or the present invention comprise a bleaching system having two essential components; a peroxygen bleach which is capable of producing hydrogen peroxide as an aqueous solution, and a bleach activator which enhances the formation of hydrogen peroxide by said peroxygen bleach.
  • the peroxygen bleach may be in any suitable form, for example, a coated particle, however, the bleach activator is in the form of a substantially cylindrically- shaped extrudate, said extrudate comprising a flowability enhancer.
  • the bleach activator containing exturdate is formed using one or more flowability enhancers which act to prevent the extrudate particles from clumping or becoming "sticky".
  • one or more binder materials are included in the bleach activator extrudates including, but not limited to, palmitic acid, a detersive surfactant, polyethylene glycol and other fatty acids and polyacrylates.
  • the peroxygen bleaching systems useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
  • Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Percarbonate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhanced surface bleaching performance.
  • Highly preferred percarbonate can be in uncoated or coated form.
  • the average particle size of uncoated percarbonate ranges from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns.
  • the preferred coating materials include mixtures of carbonate and sulphate, silicate, borosilicate, or fatty carboxylic acids.
  • the peroxygen bleaching compound will comprise at least about 0.1%, preferably from about 1% to about 75%, more preferably from about 3% to about 40%, most preferably from about 3% to about 25%, by weight of bleaching system or detergent composition.
  • the weight ratio of bleach activator to peroxygen bleaching compound in the bleaching system typically ranges from about 2:1 to 1 :5. Preferred ratios range from about 1 : 1 to about 1 :3.
  • the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to the bleach activator is greater than about 1.0, more preferably greater than about 1.5, and most preferably from about 2.0 to about 10.
  • the bleaching compositions herein comprise from about 0.5 to about 20, most preferably from about 1 to about 10, wt%. of the peroxygen bleaching compound.
  • the peroxygen bleaching compound is preferably selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and mixtures thereof. It is preferable for the detergent composition of the invention to contain less than about 3%, more preferably less than about 2.5%, and most preferably less than about 2% by weight of free water. While not wishing to be bound by theory, it is believed that by maintaining this relatively low level of free water in the composition, the propensity of the bleach activator to degrade via hydrolysis prior to use is lowered. Thus, the stability of the bleach activator is enhanced and prolonged even further as a result of a selected free water level as set forth herein.
  • the bleach activator comprising extrudate of the present invention has enhanced flowability and resistance to agglomeration or sticking. This improvement is achieved by the addition of one or more "dusting agents", "anti-agglomeration agents” or “flowability aids".
  • these flowability enhancers include alumino-silicates, magnesium silicates, fumed silica, pulverized carbonate, talc, corn starch, and the like. Any high surface are which is non-hydroscopic is suitable for use. For example, finely divided and pulverized sodium sulfate or anhydrous magnesium sulfate.
  • the flowability enhancer has a particle size of less than 10 micron (10 ⁇ ), more preferably from 1-10 ⁇ , most preferably from 3-5 ⁇ .
  • L can be essentially any suitable leaving group.
  • 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. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid.
  • a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attach by the perhydroxide anion.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize. These characteristics are generally paralleled by the pK ⁇ of the conjugate acid of the leaving group, although exceptions to this convention are known.
  • R° is an alkylene, arylene, or alkarylene group containing from about 1 to about 14 carbon atoms
  • R ⁇ is an alkyl chain containing from about 1 to about 8 carbon atoms
  • R is H or R3
  • Y is H or a solubilizing group.
  • Y is preferably selected from the group consisting of -SO3-M+, -COO-M+, -SO4-M+, (- N+R*3)X- and O- «-N(R'3), wherein R is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is an anion selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions. More preferably, Y is -SO3-M+ and -COO-M+. It should be noted that bleach activators 10
  • R is as defined above and Y is -SO3-M+ or -COO-M+ wherein M is as defined above.
  • Especially preferred bleach activators are those wherein Rl is a linear alkyl chain containing from about 6 to about 12 carbon atoms, R ⁇ is a linear alkylene chain containing from about 2 to about 6 carbon atoms, R ⁇ is H, and L is selected from the group consisting of:
  • R is H, alkyl, aryl or alkaryl. This is described in U.S. Patent 4,966,723, Hodge et al., incorporated by reference herein.
  • Preferred bleach activators are:
  • Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula, and Rl is H or an alkyl group containing from about 1 to about 4 carbon atoms. Even more preferred are bleach activators of the above general formula wherein L is as defined in the general formula and R 1 is a H.
  • Particularly preferred bleach activators are those of the above general formula wherein R is an alkyl group containing from about 5 to about 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from about 6 to about 10 carbon atoms, and L is selected from the group consisting of: 12
  • R2 ⁇ herein R is an alkyl chain containing from about 1 to about 8 carbon atoms, and Y is -SO3M+ or -COO-M+ wherein M is an alkali metal, ammonium or substituted ammonium cation.
  • R2 is as defined above and Y is -SO3M+ or -COO-M+ wherein M is as defined above.
  • the most preferred bleach activators have the formula: O
  • the bleach activator herein is sodium nonanoyloxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate (BOBS).
  • bleach activators which are particularly safe for use with machines having natural rubber parts. This is believed to be the result of not producing oily diacylperoxide (DAP) species by the perhydrolysis reaction of these amido acid-derived bleach activators, but rather forming insoluble crystalline solid 13
  • bleach activators are members selected from the group consisting of: a) a bleach activator of the general formula:
  • R is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms, R is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms, and L is a leaving group;
  • R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R--,, R.,, R 4 , and R ⁇ - may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, COOR,- (wherein R,- is H or an alkyl group) and carbonyl functions; c) N-acyl caprolactam bleach activators of the formula:
  • Preferred bleach activators of type a) are those wherein R is an alkyl group
  • bleach activators are those of the above general formulas wherein R is an alkyl group containing from about 7 to about 10 carbon atoms and R 2 contains from about 4 to about 5 carbon atoms. 14
  • Preferred bleach activators of type b) are those wherein R ⁇ , R-., R 4 , and R.- are H and R, is a phenyl group.
  • the preferred acyl moieties of said N-acyl caprolactam bleach activators of type c) have the formula R -CO- wherein R is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbons, preferably from 6 to 12 carbon atoms.
  • R is a member selected from the group consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • Amido Derived Bleach Activators employed in the present invention are amide substituted compounds of the general formulas:
  • R 5 R5 or mixtures thereof, wherein R 1 , R2 and R 5 are as defined above and L can be essentially any suitable leaving group.
  • Preferred bleach activators are those of the
  • R 3 O and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from
  • R is an alkyl chain containing from 1 to about
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • the preferred solubilizing groups are -SO-. M , -CO M , -SO 4 M ,
  • R is an alkyl chain containing from about 1 to about 4 carbon atoms
  • M is a cation which provides solubility to the bleach activator
  • X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • Preferred bleach activators are those of the above general formula wherein L is selected from the group consisting of:
  • R is as defined above and Y is -SO., M or -CO 2 M wherein M is as defined above.
  • bleach activators including those of type b) and type c), provide organic peracids as described herein by ring-opening as a consequence of the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion.
  • this ring-opening reaction in type c) activators involves attack at the caprolactam ring carbonyl by hydrogen peroxide or its anion. Since attack of an acyl caprolactam by hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl, obtaining a significant fraction of ring- opening may require a catalyst.
  • Another example of ring-opening bleach activators can be found in type b) activators, such as those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
  • Benzoxazin-type Bleach Activators Such activator compounds disclosed by Hodge include the activators of the benzoxazin-type, having the formula: 16
  • R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R ⁇ , R.-., R 4 , and R_. may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COORg (wherein R fi is H or an alkyl group) and carbonyl functions.
  • a preferred activator of the benzoxazin-type is:
  • pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching systems herein.
  • N-Acyl Caprolactam Bleach Activators - The N-acyl caprolactam bleach activators of type c) employed in the present invention have the formula:
  • R is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbons.
  • Caprolactam activators wherein the R moiety contains at least about 6, preferably from 6 to about 12, carbon atoms provide hydrophobic bleaching which affords nucleophilic and body soil clean-up, as noted above.
  • R comprises from 1 to about 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • N-acyl caprolactams are selected from the group consisting of benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, and mixtures thereof.
  • Methods for making N-acyl caprolactams are well known in the art.
  • the bleach activator is preferably not absorbed onto the peroxygen bleaching compound. To do so in the presence of other organic detersive ingredients could cause safety problems.
  • the bleach activators of type a), b) or c) will comprise at least about 0.1%, preferably from about 0.1% to about 50%, more preferably from about 1% to about 30%, most preferably from about 3% to about 25%, by weight of bleaching system or detergent composition.
  • amido-derived and caprolactam bleach activators herein can also be used in combination with rubber-safe, enzyme-safe, hydrophilic activators such as TAED, typically at weight ratios of amido-derived or caprolactam activators :TAED in the range of 1 : 5 to 5 : 1 , preferably about 1 :1.
  • the bleach activator comprising extrudates of the present invention comprise from about 0.1% to about 40% by weight of one or more binders.
  • binders include, but are not limited to, palmitic acid, detersive surfactants, polyethylene glycol, and fatty acids.
  • the substantially cylindrically- shaped extrudate comprises, by weight of the extrudate, from about 60% to about 95% of a bleach activator, from about 0.1% to about 10% of palmitic acid, from about 0.1% to about 10% of a detersive surfactant, from about 0.1% to about 10% of polyethylene glycol, and from about 0.1% to about 10% of fatty acid.
  • the binder materials in the specific extrudates gravitate or migrate toward the surface of the individual extrudate particles, thereby inhibiting excessive exposure of the bleach activator to environmental conditions such as heat and moisture prior to use.
  • the bleach activator in the substantially cylindrically-shaped extrudates do not degrade and remain stable, while 18
  • the added unanimity of particle size renders the detergent composition less susceptible to product segregation in the detergent box prior to use.
  • product segregation occurs during handling, transporting, and storing the detergent composition prior to use; the vibrating, shaking and otherwise movement of the detergent product box causes the composition to segregate by particle size.
  • the detergent composition of the present invention reduces this problem via a selected choice of particle size and shape.
  • the substantially cylindrically-shaped extrudates have mean extrudate length of from about 500 microns to about 3500 microns, more preferably from about 700 microns to about 3000 microns, and most preferably from about 900 microns to about 2500 microns.
  • the mean extrudate diameter is from about 450 microns to about 850 microns, more preferably from about 500 microns to about 800 microns, and most preferably from about 550 microns to about 750 microns.
  • the mean extrudate diameter can be measured in a variety of ways, one of which is to measure a representative sample of the extrudates using a microscope and determining the mean via calculation. The mean diameter can be determined similarly or via extrapolation from the extrusion die hole diameter.
  • the selected relatively smaller particle size and cylindrical shape of the bleach activator extrudates result in a more consistent delivery of activator to the aqueous laundering solution.
  • the variation around the target level of bleach activator to be delivered to the wash solution is unexpectedly reduced as result of using the aforementioned substantially cylindrically-shaped extrudates.
  • this allows the detergent composition to deliver the bleach activator at a more consistent level to achieve sanitization effects on the laundered fabrics.
  • Most governmental agencies require very little variation around bleach activator or other sanitizing agent target levels in order for sanitization advertising claims to be legally made to the public.
  • the invention also provides a suitable and convenient method of sanitizing fabrics which may be suitable for public advertising.
  • the number of microbes present on said fabrics is reduced by at least about 50%, more preferably reduced by at least about 90%, and most preferably reduced by at least about 99.9%.
  • This sanitizing method is interchangeably used with disinfecting, antibacterial, germ killing, odor-causing germ killing methods in accordance with the invention.
  • the specific bleach activator and peroxygen bleaching composition in the detergent composition are preferably present at specific molar 19
  • Such compositions provide extremely effective and efficient surface bleaching of textiles which thereby remove stains and/or soils from the textiles.
  • Such compositions are particularly effective at removing dingy soils from textiles.
  • Dingy soils are soils that build up on textiles after numerous cycles of usage and washing and, thus, result in a white textile having a gray tint. These soils tend to be a blend of particulate and greasy materials. The removal of this type of soil is sometimes referred to as "dingy fabric clean up”.
  • the bleach-containing detergent compositions of this invention provide such bleaching over a wide range of bleach solution temperatures. Such bleaching is obtained in bleach solutions wherein the solution temperature is at least about 5°C. Without the bleach activator, such peroxygen bleaches would be ineffective and/or impracticable at temperatures below about 60°C.
  • the percarboxylic acid then forms a reactive dimer with its anion which, in turn, evolves a singlet oxygen which is believed to be the active bleaching component. It is theorized that the singlet oxygen must be evolved at or near the textile surface in order to provide surface bleaching. Otherwise, the singlet oxygen will provide bleaching, but not at the textile surface.
  • bleaching is known as solution bleaching, i.e., the bleaching of soils in the bleach solution.
  • the longest linear alkyl chain extending from and including the carbonyl carbon of the percarboxylic acid have from about 6 to about 10 carbon atoms.
  • Such percarboxylic acids are surface active and, therefore, tend to be concentrated at the textile surface.
  • Percarboxylic acids containing fewer carbon atoms in such alkyl chain have similar redox potentials, but do not have the ability to concentrate at the textile surface. Therefore, the bleach activators within the invention are extremely efficient because much lower levels, on a molar basis, of such 20
  • bleach activators are required to get the same level of surface bleaching performance as with similar bleach activators containing fewer carbon atoms in such an alkyl chain, which are not within the invention.
  • Optimum surface bleaching performance is obtained with bleaching solutions wherein the pH of such solution is between about 8.5 and 10.5 and preferably between 9 and 10. It is preferred that such pH be greater than 9 not only to optimize surface bleaching performance, but also to prevent the bleaching solution from having an undesirable odor. It has been observed that once the pH of the bleaching solution drops below 9, the bleaching solution has an undesirable odor.
  • pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching compositions herein.
  • adjunct detergent ingredients selected from the group consisting of enzymes, soil release agents, dispersing agents, optical brighteners, suds suppressors, fabric softeners, enzyme stabilizers, perfumes, dyes, fillers, dye transfer inhibitors and mixtures thereof are included in the composition of the invention.
  • the detersive surfactants comprise at least about 0.01% by weight, preferably from about 0.1% to about 60%, more preferably from about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof.
  • a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof.
  • Water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
  • alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • anionic surfactants which suitable for use herein include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight-chain alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl 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 21
  • alkyl group contains from about 9 to about 15 carbon atoms, in straight chain, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Ci 1.13 LAS.
  • anionic surfactants suitable 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 of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Preferred essential anionic surfactants for the detergent composition are C ⁇ n 1 8 linear alkylbenzene sulfonate and C- 0 , g alkyl sulfate. If desired, low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste. Most preferred are C, 0 - g alkyl sulfates, linear or branched, and any of primary, secondary or tertiary.
  • a preferred embodiment of the present invention is wherein the surfactant paste comprises from about 20% to about 40% of a mixture of sodium C 1 0 - ⁇ linear alkylbenzene sulfonate and sodium C, -, 1 fi alkyl sulfate in a weight ratio of about 2: 1 to 1 :2.
  • Nonionic surfactants are also useful in the instant invention.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group 22
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
  • nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Preferred nonionic surfactants are of the formula R (OC HZ) OH, wherein R is a C 1 0 -C l fi alkyl group or a Cg-C 12 alkyl phenyl group, and n is from 3 to about 80.
  • Particularly preferred are condensation products of C, -,-C, ⁇ . alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C- ⁇ -C, -. alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, U.S. Patent No. 2,703,798, the disclosures of which are incorporated herein by reference.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Cationic surfactants can also be included in the present invention.
  • Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
  • Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
  • Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976, the disclosure of which is incorporated herein by reference.
  • At least one suitable adjunct detergent ingredient such as a builder is preferably included in the detergent composition.
  • the builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof.
  • Other suitable auxiliary builders are described hereinafter.
  • Preferred builders include aluminosilicate ion exchange materials and sodium carbonate.
  • the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
  • the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • the term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(Al ⁇ 2) z .(Si ⁇ 2) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula
  • These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
  • the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/- gram/gallon, and more preferably in a range from about 2 grains Ca "H" /gallon/minute/-gram/gallon to about 6 grains Ca ++ /gallon/minute/-gram gallon
  • NOBS sodium nonanoyloxybenzene sulfonate
  • 6% of palmitic acid 3% of sodium linear alkylbenzene sulfonate surfactant
  • MW polyethylene glycol
  • C9 fatty acid alumino silicate
  • zeolite A alumino silicate
  • the mixture is blended and fed to a lab extruder (Fuji Paudel Co. Ltd., Dome Granulator, DG-Ll) and extruded through dies having diameters of 350 microns
  • NOBS extrudates 500 micron 6.0 - - - diameter
  • NOBS extrudates 700 micron - 6.0 - - diameter
  • NOBS extrudates (890 micron - - 6.0 - diameter)

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Abstract

Cette invention se rapporte à une composition de détergent avec agent de blanchiment, qui renferme un composé de blanchiment au peroxygène et un activateur de blanchiment, lequel se présente sous la forme d'extrudats essentiellement cylindriques ayant une longueur moyenne comprise entre environ 500 microns et environ 3500 microns et un diamètre moyen compris entre environ 450 microns et environ 850 microns, ces extrudats comprenant un ou plusieurs agents facilitant leur aptitude à l'écoulement.
PCT/IB1999/000423 1998-03-19 1999-03-15 Composition de detergent contenant un activateur de blanchiment sous forme d'extrudats cylindriques ayant une coulabilite amelioree WO1999047633A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9908925-4A BR9908925A (pt) 1998-03-19 1999-03-15 Composição detergente que contém extrudados ativadores de alvejamento de formato cilìndrico tendo escoabilidade melhorada
JP2000536816A JP2002506923A (ja) 1998-03-19 1999-03-15 高い流動性を有する円柱形状ブリーチアクチベーター押出物を含有した洗剤組成物
EP99906389A EP1064348A1 (fr) 1998-03-19 1999-03-15 Composition de detergent contenant un activateur de blanchiment sous forme d'extrudats cylindriques ayant une coulabilite amelioree
CA002324397A CA2324397A1 (fr) 1998-03-19 1999-03-15 Composition de detergent contenant un activateur de blanchiment sous forme d'extrudats cylindriques ayant une coulabilite amelioree

Applications Claiming Priority (2)

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US4470498A 1998-03-19 1998-03-19
US09/044,704 1998-03-19

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WO1999047633A1 true WO1999047633A1 (fr) 1999-09-23

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CA (1) CA2324397A1 (fr)
WO (1) WO1999047633A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019130146A1 (fr) * 2017-12-29 2019-07-04 Zobele Holding S.P.A. Additif de blanchisserie pour éliminer les taches

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Publication number Priority date Publication date Assignee Title
CN103911852B (zh) * 2013-12-16 2016-07-27 高阳县格瑞恩染织有限公司 一种棉纤维活化剂及其制备方法
CN109972382A (zh) * 2019-03-01 2019-07-05 杨明忠 一种安全高效彩漂液的制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4399049A (en) * 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
EP0299599A1 (fr) * 1987-05-12 1989-01-18 Warwick International Group Limited Compositions d'activateurs de blanchiment
EP0375241A2 (fr) * 1988-12-22 1990-06-27 The Procter & Gamble Company Coloration d'activateurs de blanchiment stabilisés en forme d'extrudats
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE4143016A1 (de) * 1991-12-24 1993-07-01 Henkel Kgaa Bleichaktivatoren in granulatform (ii)
DE19537980A1 (de) * 1995-10-12 1997-04-17 Henkel Kgaa Bleichaktivatoren in Granulatform (III)
WO1997027280A1 (fr) * 1996-01-29 1997-07-31 The Procter & Gamble Company Procede de fabrication d'activateurs de blanchiment particulaires
US5795854A (en) * 1997-11-20 1998-08-18 The Procter & Gamble Company Detergent composition containing cylindrically-shaped bleach activator extrudates

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4399049A (en) * 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
EP0299599A1 (fr) * 1987-05-12 1989-01-18 Warwick International Group Limited Compositions d'activateurs de blanchiment
EP0375241A2 (fr) * 1988-12-22 1990-06-27 The Procter & Gamble Company Coloration d'activateurs de blanchiment stabilisés en forme d'extrudats
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE4143016A1 (de) * 1991-12-24 1993-07-01 Henkel Kgaa Bleichaktivatoren in granulatform (ii)
DE19537980A1 (de) * 1995-10-12 1997-04-17 Henkel Kgaa Bleichaktivatoren in Granulatform (III)
WO1997027280A1 (fr) * 1996-01-29 1997-07-31 The Procter & Gamble Company Procede de fabrication d'activateurs de blanchiment particulaires
US5795854A (en) * 1997-11-20 1998-08-18 The Procter & Gamble Company Detergent composition containing cylindrically-shaped bleach activator extrudates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019130146A1 (fr) * 2017-12-29 2019-07-04 Zobele Holding S.P.A. Additif de blanchisserie pour éliminer les taches

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JP2002506923A (ja) 2002-03-05
CN1301295A (zh) 2001-06-27
CA2324397A1 (fr) 1999-09-23
EP1064348A1 (fr) 2001-01-03
AR014741A1 (es) 2001-03-28
BR9908925A (pt) 2000-11-21

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