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EP1032639A1 - Composition detergente contenant des particules activatrices de blanchiment a taille optimale - Google Patents

Composition detergente contenant des particules activatrices de blanchiment a taille optimale

Info

Publication number
EP1032639A1
EP1032639A1 EP98966939A EP98966939A EP1032639A1 EP 1032639 A1 EP1032639 A1 EP 1032639A1 EP 98966939 A EP98966939 A EP 98966939A EP 98966939 A EP98966939 A EP 98966939A EP 1032639 A1 EP1032639 A1 EP 1032639A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
microns
bleach activator
sodium
carbon atoms
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.)
Withdrawn
Application number
EP98966939A
Other languages
German (de)
English (en)
Inventor
Adrian John Waynforth Angell
Joseph Adam Pauley
Steven Matthew Gabriel
Donald Ray Brown
Michael Eugene Burns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US08/974,784 external-priority patent/US5795854A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1032639A1 publication Critical patent/EP1032639A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/391—Oxygen-containing 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
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds

Definitions

  • the invention relates to a detergent composition containing a peroxygen bleaching compound and bleach activator particles having a selected particle size for improved stability and performance.
  • Typical bleaching compositions contain peroxygen bleaches capable of yielding hydrogen peroxide in aqueous solutions and bleach activators to enhance bleach performance. It has long been known that peroxygen bleaches are effective for stain and/or soil removal from textiles, 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.
  • peroxygen bleaches are only partially effective and, therefore, in order to obtain a desirable level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. This is economically impracticable for large-scale commercialization of modern detergent products.
  • peroxygen bleaches are rendered inefifective, regardless of the level of peroxygen bleach added to the system.
  • 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.
  • bleach activators that render peroxygen bleaches effective at bleach solution temperatures below 60°C.
  • the invention provides a detergent composition containing a peroxygen bleaching compound and a bleach activator in the form of particles, preferably in the form of substantially cylindrically-shaped extmdates, having a selected relatively small particle size.
  • the smaller sized bleach activator particles 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. Additionally, the bleach activator particles have acceptable flow properties and allow the detergent composition to deliver sanitization effects to the laundered fabrics more consistently.
  • the term "particles” refer to agglomerates, flakes, extmdates, or other shaped particles.
  • the phrase "cylindrically-shaped extmdates” means an extruded particle having a surface shape generated by a straight line moving parallel to a fixed straight line and intersecting a fixed planar closed curve.
  • An "effective amount" of a detergent composition containing a bleach activator is any amount capable of measurably improving both soil removal from and sanitization of the fabric when it is washed by the consumer. In general, this amount may vary quite widely.
  • the terms "disinfecting”, “disinfection”, “antibacterial”, “germ kill”, and “sanitization” are intended to mean lolling microbes commonly found in and on fabrics requiring laundering. Examples of various microbes include germs, bacteria, viruses, parasites, and fungi/spores.
  • "free water” level means the level on a percentage by weight basis of water in the detergent composition which is not bound up or in another detergent ingredient such as zeolite; it is the water level in excess of any water entrained in, adsorbed in, or otherwise bound up in other detergent ingredients.
  • a bleach-containing detergent composition comprises: (a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; (b) a bleach activator having the general 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 12 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, wherein the molar ratio of hydrogen peroxide yielded by (a) to bleach activator (b) is greater than about 1.0, and said bleach activator is in the form of a particles having a mean particle diameter of from about 200 microns to about 2000 microns.
  • a method of using the detergent composition to sanitize fabrics comprises the step of contacting said fabrics with an effective amount of a detergent composition as described herein in an aqueous solution to sanitize the fabrics. All percentages and ratios used herein are expressed as percentages by weight (anhydrous basis) unless otherwise indicated. All cited documents are incorporated herein by reference.
  • a detergent composition containing 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 composition of the invention essentially comprises two components, namely, a peroxygen bleaching compound and a bleach activator in the form of particles having a specified mean particle diameter.
  • the particles are in substantially cylindrically-shape extrudate form.
  • the peroxygen bleaching compound is capable of yielding hydrogen peroxide in an aqueous solution.
  • the detergent composition of the invention is unexpectedly stable with respect to the bleach activator in terms of maintaining or not degrading over extended storage periods prior to use.
  • one or more binder materials are included in the bleach activator particles or extmdates including, but not limited to, palmitic acid, a detersive surfactant, polyethylene glycol and other fatty acids and polyacrylates.
  • the binder materials in the specific particles or extmdates gravitate or migrate toward the surface of the individual particles, thereby inhibiting excessive exposure of the bleach activator to environmental conditions such as heat and moisture prior to use.
  • the bleach activator particles including those that are substantially cylindrically-shaped extmdates do not degrade and remain stable, while also bearing a particle size closely mirroring the size of the other detergent ingredients in the detergent composition.
  • the added unanimity of particle size renders the detergent composition less susceptible to product segregation in the detergent box prior to use.
  • detergent composition of the present invention reduces this problem via a selected choice of particle size and shape.
  • the mean particle diameter of the particles are from about 200 microns to about 2000 microns, more preferably from about 300 microns to about 1000 microns, and most preferably from about 350 microns to about 750 microns. More preferably, the particles are substantially cylindrically-shaped extmdates having a mean extmdate 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 extmdate 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 particle and extmdate diameters can be measured in a variety of ways, one of which is to measure a representative sample of the extmdates 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.
  • a finely divided inorganic powder may be added as a flow aid to the surface of the particles.
  • This flow aid includes, but is not limited to, finely divided aluminosilicates, silicas, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, sodium carbonate, and mixtures thereof. It is preferable for the level of the flow aid to be from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1.5% to about 5% by weight of the detergent composition. The most preferable flow aid is aluminosilicate.
  • 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 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 extmdates.
  • 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 ratios of hydrogen peroxide to bleach activator.
  • 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 ofparticulate 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 12 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 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.
  • the substantially cylindrically-shaped extmdate comprises, by weight of the extmdate, 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 bleach activator for the bleaching systems useful herein preferably has the following structure:
  • 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 12 carbon atoms and L is a leaving group, the conjugate acid of which has a pK ⁇ in the range of from about 4 to about 13, preferably from about 6 to about 11, most preferably from about 8 to about 11.
  • 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.
  • Preferred bleach activators are those of the general formula:
  • R* is an alkyl group containing from about 6 to about 12 carbon atoms
  • R2 is an alkylene containing from 1 to about 6 carbon atoms
  • R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms
  • L is selected from the group consisting of:
  • R*> is an alkylene, arylene, or alkarylene group containing from about 1 to about 14 carbon atoms
  • R 3 is an alkyl chain containing from about 1 to about 8 carbon atoms
  • R4 is H or R 3
  • Y is H or a solubilmng group.
  • Y is preferably selected from the group consisting of -SO3T ⁇ T, -COO " M ⁇ -CO 2 H, -CO 2 " M ⁇ -SO4 " M * , (-N+R'3)X " and O ⁇ -N(R'3), wherein R 1 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 -803 ⁇ , -CO H and -COO " M ⁇ It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleach solution in order to assist in their dissolution. Preferred
  • R is as defined above and Y is -803 ⁇ * or -COO " M + wherein M is as defined above.
  • Especially preferred bleach activators are those wherein R 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:
  • R3 is as defined above, Y is -803 ⁇ or -COO ' M and M is as defined above.
  • a preferred bleach activator is:
  • R 1 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:
  • R! is H or an alkyl group containing from about 1 to about 6 carbon atoms and R2 is an alkyl group containing from about 1 to about 6 carbon atoms and L is as defined above.
  • Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula, and R* 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* is a H.
  • More preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and L is selected from the group consisting of:
  • R, R ⁇ , R 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 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 12 carbon atoms, and L is selected from the group consisting of:
  • R2 is an alkyl chain containing from about 1 to about 8 carbon atoms
  • Y is -SOa ' M * or -COCM * wherein M is an alkali metal, ammonium or substituted ammonium cation.
  • Especially preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and L is selected from the group consisting of:
  • R 2 is as defined above and Y is -SOs * , -COO ' M * , or -CO 2 H, wherein M is as defined above.
  • the most preferred bleach activators have the formula:
  • R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and M is sodium or potassium.
  • the bleach activator herein is sodium nonanoyloxybenzenesulfonate (NOBS), sodium benzoyloxybenzenesulfonate (BOBS), sodium lauroyloxybenzene sulfonate (LOBS) or para-decanoyloxybenzoic acid (DOBA).
  • bleach activators which are particularly safe for use with machines having natural bber 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 DAP's. These solids are believed to not form a coating film and thus natural mbber parts are not exposed to DAP's for extended periods of time.
  • DAP oily diacylperoxide
  • These preferred bleach activators are members selected from the group consisting of: a) a bleach activator of the general formula:
  • R5 R5 or mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group
  • 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 Re may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, COORg (wherein R, is H or an alkyl group) and carbonyl functions; c) N-acyl caprolactam bleach activators of the formula:
  • R is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons; and d) mixtures of a), b) and c).
  • 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
  • Preferred bleach activators of type b) are those wherein R2, R>, R 4 , and R 5 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:
  • bleach activators are those of the above general formula wherein R 1 , R2 and R 5 are as defined for the peroxyacid and L is selected from the group consisting of:
  • 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 2 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 3 ⁇ M , -CO2 ⁇ M , or -CO 2 H, wherein
  • 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: wherein R, is H, alkyl, alkaryl, aryl, arylalkyl, and wherein I , R j , R 4 , and R * may be the same or different substituents selected from H, halogen, alkyl, alkenyl,
  • 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 R comprises from 1 to about 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • Mixtures of hydrophobic and hydrophilic caprolactams, typically at weight ratios of 1 :5 to 5 : 1 , preferably 1:1, can be used herein for mixed stain removal benefits.
  • 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 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.
  • bleach activator/bleaching compound systems herein are useful per se as bleaches. However, such bleaching systems are especially useful in compositions which can comprise various detersive adjuncts such as surfactants, builders and the like.
  • 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 following are representative examples of the detergent surfactants useful in the present detergent composition.
  • 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.
  • Particulariy 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.
  • Additional 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.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Co j g 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, 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 C ⁇ j_i3 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 CJQ ⁇ o linear alkylbenzene sulfonate and C jQ _, « alkyl sulfate.
  • low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste.
  • Most preferred are C, Q , « 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 10 _ 1 linear alkylbenzene sulfonate and sodium C, ⁇ 1 fi alkyl sulfate in a weight ratio of about 2: 1 to 1 :2.
  • Water-soluble 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 can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • 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 2 H 4 ) OH, wherein R is a jQ -Cig alkyl group or a Cg-C « 2 alkyl phenyl group, and n is from 3 to about 80.
  • Particulariy preferred are condensation products 0I* j2 -C j r alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C, 2 -C, 3 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.
  • particle size diameter 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).
  • 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 [(AlO 2 ) z .(SiO 2 ) y ]xH2 ⁇ 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
  • 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 K ummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
  • 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.
  • 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 ++ /gallon/minute/-gram/gallon to about 6 grains Ca ++ /gallon/minute/-gram/gallon.
  • NOBS extmdates 500 micron 6.0 - - - diameter
  • NOBS extmdates 700 micron - 6.0 - - diameter
  • NOBS extmdates (350 micron - - - 6.0 diameter)
  • NOBS extmdates (890 micron - - 6.0 - diameter) Free water 2.0 2.0 2.0 2.0 2.0 2.0 2.0
  • Example I, II, HI and IV compositions are tested for bleach activator storage stability and product segregation tendency according to the following test method described in detail hereinafter.
  • Two funnels are set up on a ring stand with the stem on top such that there is a distance of 37 cm between the neck of the top funnel and the bottom of the lower funnel and there is enough space to position a small jar under the lower funnel;
  • the Coning Index (CI) 100x(highest activator level - lowest activator level)/mean activator level, wherein the higher the CI, the greater the segregation tendency.
  • NOBS extmdates are prepared in the same manner except the extmdates have a mean diameter of 850 microns. Thereafter, three batches of NOBS extmdates are ground in a Quadro CO-Mill to form extmdates having a mean length of 4000 microns (Example V), 2000 microns (Example VI) and 1000 microns (Example VII), respectively. Each batch is blended into a bleach-containing detergent composition as exemplified in above in Examples I-IV. The activator stability and segregation tendency tests are conducted as in Examples I-IV. The results indicate that Examples VI and VII which are within the scope of the invention all unexpectedly have excellent stability and product segregation properties, whereas comparative Example V having a mean extmdate length outside the invention has an unacceptable segregation potential.
  • LOBS sodium lauroyloxybenzene sulfonate
  • DOB A "DOB A" extmdates are prepared in the same manner as Example I and are contained in identical formulas as Example I except NOBS is replaced with DOB A.
  • Example XII 1000 microns
  • Example XHI 1000 microns
  • Examples I-IV The activator stability and segregation tendency tests are conducted as in Examples I-IV. The results indicate that Examples Xm and XII which are within the scope of the invention all unexpectedly have excellent stability and product segregation properties, whereas comparative Example XI having a mean extmdate length outside the invention has an unacceptable segregation potential.
  • a 2 L three-necked round-bottomed flask is fitted with a mechanical stirrer, reflux condenser, and gas inlet tube.
  • the flask is charged with lauroyl chloride (2, Aldrich, 96g, 0.44 mol), toluene (500 mL), and anhydrous phenol sulfonate (3, 78g, 0.40 mol).
  • lauroyl chloride 2, Aldrich, 96g, 0.44 mol
  • toluene 500 mL
  • anhydrous phenol sulfonate 3, 78g, 0.40 mol
  • a 2 L beaker is fitted with a mechanical stirrer, pH electrode, and temperature probe.
  • the beaker is charged with p-hydroxybenzoic acid (5, Aldrich, 138g, 1.0 mol) and IN sodium hydroxide (1.0 L, 1.0 mol), resulting in a solution having a pH of 11.2.
  • This solution is cooled to 10° C and decanoyl chloride (6, Aldrich, 95g, 0.5 mol) dissolved in 250 mL of diethyl ether is added dropwise at 0-15° C over a period of 15 min while maintaining the pH at 10 with concurrent addition of 50% sodium hydroxide solution.
  • the solution pH is 10.1 and the solution temperature was 10° C.

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Abstract

Composition détergente contenant un agent de blanchiment, qui comporte un composé de blanchiment péroxygéné et un activateur de blanchiment. L'activateur de blanchiment se présente sous forme de particules ayant un diamètre moyen de 200 microns à 2000 microns. La présente invention concerne également des particules activatrices de blanchiment se présentant comme des produits d'extrusion de forme pratiquement cylindrique dont la longueur moyenne est d'environ 500 microns à environ 3500 microns et le diamètre moyen d'environ 450 microns à environ 850 microns.
EP98966939A 1997-11-20 1998-09-23 Composition detergente contenant des particules activatrices de blanchiment a taille optimale Withdrawn EP1032639A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US974784 1997-11-20
US08/974,784 US5795854A (en) 1997-11-20 1997-11-20 Detergent composition containing cylindrically-shaped bleach activator extrudates
US93834 1998-06-08
US09/093,834 US5891838A (en) 1997-11-20 1998-06-08 Detergent composition containing optimally sized bleach activator particles
PCT/US1998/019999 WO1999027061A1 (fr) 1997-11-20 1998-09-23 Composition detergente contenant des particules activatrices de blanchiment a taille optimale

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BR9908925A (pt) * 1998-03-19 2000-11-21 Procter & Gamble Composição detergente que contém extrudados ativadores de alvejamento de formato cilìndrico tendo escoabilidade melhorada
DE10134364A1 (de) 2001-07-14 2003-01-23 Clariant Gmbh Verfahren zur Herstellung von Bleichaktivator-Granulaten
DE10136805A1 (de) 2001-07-25 2003-02-13 Clariant Gmbh Verfahren zur Herstellung von Bleichaktivator-Granulaten
EP2292725B2 (fr) 2009-08-13 2022-08-24 The Procter & Gamble Company Procédé de nettoyage de tissus à basse température
DE102010034243A1 (de) * 2010-08-13 2012-02-16 Clariant International Limited Verfahren zur Herstellung von Acyloxybenzoesäuren
DE102010034244A1 (de) * 2010-08-13 2012-02-16 Clariant International Limited Verfahren zur Herstellung von Acyloxybenzoesäuren
MX2020013602A (es) * 2018-06-15 2021-03-09 Procter & Gamble Composiciones de detergente para lavanderia particuladas que comprenden particulas de perfume y metodo de uso de estas.

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AT339246B (de) * 1974-08-14 1977-10-10 Henkel & Cie Gmbh Als bestandteil von pulverformigen wasch- und bleichmitteln geeignetes bleichhilfsmittel
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US5458801A (en) * 1991-09-27 1995-10-17 Kao Corporation Process for producing granular bleach activator composition and granular bleach activator composition
ATE169003T1 (de) * 1993-05-20 1998-08-15 Procter & Gamble Bleichmittel, welche einen substituierten benzoyl caprolactam bleichaktivator enthalten
US5405413A (en) * 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
US5762647A (en) * 1995-11-21 1998-06-09 The Procter & Gamble Company Method of laundering with a low sudsing granular detergent composition containing optimally selected levels of a foam control agent bleach activator/peroxygen bleaching agent system and enzyme
TR199801458T2 (xx) * 1996-01-29 1998-10-21 The Procter & Gamble Company Par�ac�k halinde a�artma aktivat�r bile�eninin yap�lmas� i�in i�lem.
ATE263230T1 (de) * 1996-06-28 2004-04-15 Procter & Gamble Bleichmittelvorläuferzusammensetzungen

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Title
See references of WO9927061A1 *

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CA2311378A1 (fr) 1999-06-03
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CA2311378C (fr) 2004-04-20
CN1130456C (zh) 2003-12-10

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