EP0105690A1 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
EP0105690A1
EP0105690A1 EP83305726A EP83305726A EP0105690A1 EP 0105690 A1 EP0105690 A1 EP 0105690A1 EP 83305726 A EP83305726 A EP 83305726A EP 83305726 A EP83305726 A EP 83305726A EP 0105690 A1 EP0105690 A1 EP 0105690A1
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group
bleaching
aryl
compositions
carbon atoms
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EP83305726A
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EP0105690B1 (fr
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John C. Dyer
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Procter and Gamble Co
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Procter and Gamble Co
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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

Definitions

  • This invention relates to bleaching compositions. More particularly, this invention relates to bleaching compositions that provide effective and efficient solution bleaching and/or surface bleaching performance on textiles.
  • Solution bleaching is bleaching wherein the bleaching mechanism takes place in the bleaching solution itself, i.e., the bleach and water mixture, rather than the textile surface, and, thereby, modifies soils that are suspended in the bleaching solution. This prevents soils from being deposited on the textile surface and/or decolorizes soils which are then deposited on the textile surface, but are rendered less objectionable.
  • Surface bleaching is bleaching wherein the bleaching mechanism takes place on the textile surface and, thereby, modifies stains that are on the textile surface. This results in the removal and/or decoloration of such stains.
  • the bleaching compositions within the invention contain a peroxycarboxylic acid and an aromatic sulfonyl halide bleach activator.
  • the bleaching compositions within the invention are detergent compositions.
  • peroxygen bleaches that yield hydrogen peroxide in an aqueous solution provide a desirable level of solution bleaching and/or surface bleaching performance, but that they are also extremely temperature dependent.
  • Such bleaches are essentially only practicable and/or effective in bleaching solutions wherein the solution temperature is above about 60°C.
  • At bleach solution temperatures of about 60°C peroxygen bleaches are only partially effective, due to their low level of reactivity. Therefore, in order to obtain a desirable level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. As the bleach solution temperature is lowered below 60°C, even higher levels of peroxygen bleach must be added to the system in order to obtain a desirable level of bleaching performance.
  • peroxygen bleaches are commonly used as a detergent adjuvant in textile wash processes that utilize an automatic household washing machine at wash water temperatures below 60°C. Such wash temperatures are utilized because of textile care and energy considerations.
  • bleach activators that render peroxygen bleaches effective at bleach solution temperatures below 60°C. Numerous substances have been disclosed in the art as effective bleach activators.
  • the substances that have been utilized as bleach activators are substances that react with the perhydroxide anion of hydrogen peroxide, which is yielded by the peroxygen bleach in the bleaching solution, to form a peroxy acid.
  • Peroxy acids are more reactive than the peroxygen bleach alone and, therefore, can provide bleaching at bleach solution temperatures below about 60°C.
  • Many of the peroxy acids are peroxycarboxylic acids or persulfonic acids.
  • the peroxycarboxylic acids are derived from bleach activators that contain a carbonyl carbon that reacts with the perhydroxide anion to form the peroxycarboxylic acid. Examples of such bleach activators are disclosed in U.S.
  • the persulfonic acids are derived from bleach activators that contain a sulfonyl group that reacts with the perhydroxide anion to form the persulfonic acid.
  • U.S. Patent 4,292,191, Gray discloses bleaching compositions containing a peroxygen bleach and a sulfonyl halide bleach activator, such as an alkoxybenzenesulfonyl halide.
  • U.S. Patent 4,107,065, Gray (August 15, 1978) discloses bleaching compositions containing a peroxygen bleach and a sulfonyl bleach activator, such as an aromatic sulfonyl halide.
  • the present invention comprises a bleaching composition containing:
  • This invention relates to bleaching compositions consisting of a peroxycarboxylic acid and an aromatic sulfonyl halide bleach activator, both of which are defined hereinafter.
  • the bleaching compositions provide very effective and efficient solution bleaching and/or surface bleaching performance on textiles.
  • Solution bleaching is particularly beneficial when the bleaching compositions are detergent compositions. This is because a detergent system may be effective for removing soils from the textiles and into the bleaching solution, but not for preventing such soils from being redeposited onto the textiles.
  • Solution bleaching modifies the soils in the bleaching solution and, thereby, reduces such soil redeposition and/or decolorizes the soils which renders soil redeposition less objectionable.
  • the surface bleaching provided by the bleaching compositions not only provides effective and efficient removal and/or decoloration of stains on textiles, but also provides dingy soil removal.
  • 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 body lipids and proteinaceous debris. The removal of this type of soil is sometimes referred to as "dingy fabric clean up”.
  • solution bleaching and/or surface bleaching performance is obtained with minimal damage to the textiles and with bleach solution temperatures as low as about 5°C.
  • Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bteach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator are also able to provide solution bleaching and/or surface bleaching at temperatures below about 60°C, i.e., the temperature wherein peroxygen bleaches are essentially ineffective; however, they provide neither the effectiveness nor the efficiency of the bleaching compositions within the invention.
  • the bleaching compositions within the invention are extremely effective. Such compositions provide a superior level of solution bleaching and/or surface bleaching performance over a very wide class of stains.
  • Bleaching compositions consisting of only a peroxycarboxylic acid or, especially, a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator do not provide the superior level of bleaching performance over a very wide class of stains.
  • Bleaching compositions consisting only of a peroxycarboxylic acid provide, at best, a superior level of bleaching performance for only a narrow class of stains. Such performance is obtained primarily on beverage type stains, e.g., tea and wine.
  • the bleaching compositions within the invention are very efficient. Extremely small quantities of such compositions provide the superior level of solution bleaching and/or surface bleaching performance. Without being bound by theory, it is believed that such efficiency is obtained because a substantial majority of active oxygen, defined below, is utilized for bleaching during the bleaching process. This can be explained as follows.
  • the peroxycarboxylic acid reacts with the aromatic sulfonyl halide bleach activator to form an acyl persulfonate.
  • the acyl persulfonate contains an -0-0- group it contains a reactive oxygen atom, generally referred to as an "active oxygen" atom.
  • the active oxygen is the active bleaching component which reacts with and, thereby, modifies stains on textiles and/or soils in the bleaching solution.
  • the acyl persulfonate is sufficiently reactive so that very little active oxygen is present after the bleaching process.
  • the acyl persulfonate is not too reactive, based upon the superior level of solution bleaching and/or surface bleaching performance observed, so as to decompose rather than provide such bleaching performance. Therefore, the vast majority of the active oxygen is utilized for bleaching during the bleaching process. This enables one to obtain the superior level of bleaching performance with very small amounts of the bleaching compositions within the invention.
  • Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator are extremely inefficient and/or ineffective.
  • Bleaching compositions consisting only of a peroxycarboxylic acid are very inefficient because a substantial amount of the active oxygen of the peroxycarboxylic acid remains in the bleaching solution after the bleaching process is carried out. This unreacted peroxycarboxylic acid is essentially wasted.
  • very large amounts of such compositions as compared to the bleaching compositions within the invention, are required.
  • bleaching compositions consisting of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator are very efficient in that very little active oxygen is present after the bleaching process.
  • bleaching compositions do not provide the desired superior level of solution bleaching performance and provide essentially no surface bleaching.
  • the persulfonic acid formed is so reactive that it decomposes before it even comes into contact with the textiles. Only the bleaching compositions within the invention are both efficient and provide the superior level of solution bleaching and/or surface bleaching performance over a very wide class of stains.
  • bleaching compositions within the invention provide the superior level of solution bleaching and/or surface bleaching performance over a very wide range of pH's of the bleaching solution. Therefore, for example, when the bleaching compositions are detergent compositions one can adjust the pH of the bleaching solution so as to optimize detergency performance without sacrificing bleaching performance.
  • Typical activated bleaching compositions i.e., those consisting only of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and a bleach activator which react in the bleaching solution to form a peroxy acid, are very pH dependent.
  • the initial pH of the bleaching solution containing the bleaching compositions within the invention is from 6 to
  • the ratio of the peroxycarboxylic acid to aromatic sulfonyl halide is such that the molar ratio of each actual and potential peroxycarboxyl group of the peroxycarboxylic acid to each sulfonyl group of the aromatic sulfonyl halide that can potentially generate acyl persulfonate is from 10 to 0.05, preferably from 1 to .3 and most preferably from 1 to 0.7. Molar ratios of such components of from 1 to 0.7 are most preferred because vast excesses of either component will result in such excess not interacting with the other component and, therefore, won't provide the superior level of bleaching performance that is obtained by such components that interact with each other.
  • any peroxycarboxylic acid or salt thereof is suitable for use herein. Albeit some peroxycarboxylic acids are more preferred than others, it is believed that the effectiveness and efficiency of solution bleaching and/or surface bleaching performance of essentially any peroxycarboxylic acid will be enhanced by utilizing it in the bleaching compositions within the invention.
  • the preferred peroxycarboxylic acids and salts thereof have the general formula: wherein R is selected from H, a linear or branched alkyl or alkylene group containing from 1 to 18 carbon atoms, a cyclic alkyl, or alkylene group containing from
  • M is H or a cation which provides water-solubility or dispersibility to the peroxycarboxylic acid and r is from 1 to the total number of hydrogen atoms on R.
  • M is H or an alkali metal or an alkaline earth metal, with H, magnesium, sodium and potassium being the most preferred.
  • R can be substituted with essentially any group or groups, including an alkyl group when R is aryl and an aryl group when R is alkyl, so long as they do not interfere with the function of the peroxycarboxylic acid.
  • the preferred alkyl or alkylene group substituents are -S03M and -COOM and the preferred aryl and arylene substituents are selected from halogens (fluorine, chlorine, or bromine), -N0 2 , -OCH 3 and -COOM wherein M is as defined above.
  • Suitable aromatic heterocyclic groups include furan, thiophene and pyridine. Examples of polyarylene groups consisting of two or more annelated benzenoid rings are the napthyl, phenanthryl and anthracenyl moieties.
  • the more preferred peroxycarboxylic acids and salts thereof have the qeneral formula: wherein A is a halogen (fluorine or chlorine) or -NO2, M is as defined above, T is an alkyl group containing from 5 to 18 carbon atoms and r is one or two.
  • peroxycarboxylic acids and salts thereof have the general formula: wherein A is a halogen (chlorine or fluorine), preferably Cl, and M is H or magnesium.
  • A is a halogen (chlorine or fluorine), preferably Cl
  • M is H or magnesium.
  • the peroxycarboxylic acid can be formed in situ from its precursors.
  • a two component peroxycarboxylic acid source consisting of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and a bleach activator that contains a carbonyl carbon that can potentially react with the hydrogen peroxide to form a peroxycarboxylic acid can be utilized.
  • This system within the compositions of the invention provides essentially the same level of effectiveness and efficiency of solution bleaching and/or surface bleaching performance as is obtained by directly utilizing a peroxycarboxylic acid within the compositions of the invention.
  • the pH of the bleaching solution need not be similar to the pK of the peroxycarboxylic acid. Therefore, one can adjust the pH of the bleaching solution to maximize the formation of the perhydroxide anion and, thus, maximize the formation of the peroxycarboxylic acid.
  • the peroxygen bleaches useful herein are those capable of yielding hydrogen peroxide in an aqueous solution. These bleaches 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 bleaches, such as the alkali metal perborates, percarbonates, perphos- phates, and the like. Mixtures of two or more such bleaches can also be used, if desired.
  • Preferred peroxygen bleaches include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate monohydrate and sodium perborate tetrahydrate and mixtures thereof.
  • the bleach activators that can be utilized for such a purpose are ones capable of generating peroxycarboxylic acids and have the general formula: wherein R is as defined above and L is a leaving group, wherein the conjugate acid of the anion formed on L has a pK a in the range of from 4 to 13.
  • 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, as discussed hereinabove, is the perhydrolysis reaction. Leaving groups that exhibit such behavior are those in which their conjugate acid has a pK a in the range of from 4 to 13, preferably from 7 to 11 and most preferably from 8 to 11.
  • R or L can be a group that contains an aromatic sulfonyl halide.
  • a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and provides the desired level of solution bleaching and/or surface bleaching performance.
  • Preferred bleach activators are those of the above general formula wherein R is as defined above and L is selected from wherein R is as defined above, R 2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R is H or R 2 , and Z is H or a solubilizing group.
  • the preferred solubilizing groups are -SO - 3 M + , -COO - M + , -SO - 4 M + , (-N + R 3 4 )X - and O ⁇ NR 2 4 and most preferably -SO - 3 M + and -COO M wherein R is an alkyl chain containing from about 1 to about 4 carbon atoms, M is as defined above and X is an anion which provides solubility to the bleach activator.
  • X is a halide (fluorine, chlorine or bromine), hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • the molar ratio of hydrogen peroxide yielded by the peroxygen bleach to such peroxycarboxylic acid generating bleach activator is from 20 to 0.1 , preferably from 3 to 1 and most preferably from 2 to 1. However, it should be noted that the preferred ratio is found to vary considerably if the initial pH of the bleaching solution is below 9. Under such conditions a higher molar ratio of hydrogen peroxide yielded by the peroxygen bleach to peroxycarboxylic acid generating bleach activator is desirable. Preferably, such molar ratio is from 4 to 20.
  • Another precursor that can be utilized to form the peroxycarboxylic acid in situ is an organic peroxide compound. It is believed that such a compound undergoes hydrolysis in the bleaching solution to form the peroxycarboxylic acid. This system is not preferred because the peroxycarboxylic acid formation is often slow and, therefore, it is theorized that during this time some of the aromatic sulfonyl halide bleach activator undergoes hydrolysis to form an inactive sulfonic acid.
  • organic peroxide compounds have the general formula: wherein each R is as defined above.
  • a peroxygen bleach such as those described above, can also be added to the bleaching solution with the organic peroxide compound.
  • the molar ratio of such organic peroxide compounds to such peroxygen bleach is from 0.1 to 10, preferably from 0.25 to 4 and most preferably from 1 to 0.3.
  • the level of peroxycarboxylic acid within compositions of the invention is from 0.1% to 80%, preferably from 5% to 60% and most preferably from 30% to 60%. It should be noted that when a two component peroxycarboxylic acid source is utilized, e.g., a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus a peroxycarboxylic acid generating bleach activator or such peroxygen bleach plus an organic peroxide compound, the level of each component should be such that it can theoretically produce the levels of peroxycarboxylic acid within the compositions of the invention. When the bleaching compositions within the invention are also detergent, compositions it is preferred that the level of peroxycarboxylic acid is from 0.1% to 10% and more preferably from 1% to 3%.
  • aromatic sulfonyl halide bleach activator Essentially any aromatic sulfonyl halide bleach activator is suitable for use herein.
  • the aromatic group can contain one or more substituents so long as they do not interfere with the function of the bleach activator.
  • each Y is selected from halogens and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to 12 and each n 2 is from 0 to 18, E is selected from the group consisting of an aryl arylene group, an aromatic heterocyclic group. two or more annelated benzenoid rings and groups in which two or more aryl arylene substituents are covalently attached, Q is a halogen (fluorine, chlorine, or bromine) preferably chlorine, and each n is from 1 to 3.
  • Suitable aromatic heterocyclic groups include furan, thiophene, quinoline and pyridine.
  • Examples of polyarylene groups consisting of two or more annelated groups are the napthyl, phenanthryl and anthracenyl moieties.
  • the preferred aromatic sulfonyl halide bleach activators are selected from
  • the most preferred aromatic sulfonyl halide bleach activator has the formula:
  • the level of aromatic sulfonyl halide within the compositions of the invention is from .1% to 70%, preferably from 5% to 70% and most preferably from 40% to 70%.
  • the level of aromatic sulfonyl halide is from 0.1% to 10% and more preferably from 1% to 3%.
  • the bleaching compositions of the invention can be detergent compositions.
  • the bleaching compositions can contain typical detergent composition components such as detergency surfactants and detergency builders. In such preferred embodiments the bleaching compositions are particularly effective.
  • the bleaching compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al. Such components include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
  • the detergent surfactants can be any one or more surface active agents selected from anionic, nonionic, zwitterionic, amphoteric and cationic classes and compatible mixtures thereof.
  • Detergent surfactants useful herein are listed in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • 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.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 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 (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the ' type described in U.S. Patents 2,220,099 and 2,477,383.
  • Espec- lally 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 11-13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from
  • alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from
  • Water-soluble nonionic surfactants are also useful in the compositions of the invention.
  • Such nonionic materials include compounds produced by the condensation of alkyl or 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 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics 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 2 to 12 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of
  • 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 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 8 to 18 carbon atoms.
  • the level of detergent surfactant that can be employed is from 0% to about 50%, preferably from 1% to 30% and most preferably from 10% to 25% by weight of the total composition.
  • detergency builders can be employed in the bleaching compositions.
  • Water-soluble inorganic or organic electrolytes are suitable builders.
  • the builder can also be water-insoluble calcium ion exchange materials; nonlimiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates. Specific examples of such salts include sodium and potassium tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.
  • suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and aminopotyace- tates, for example, nitrilotriacetates, glycinates, ethylenediamine tetraacetates, N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium -and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium, and lithium salts of ethane-1-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid: and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxy- methyloxysuccinic acid, 2-oxa-1 1 ,3-propane tricarboxylic acid, 1,1,2,2-ethane
  • a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in U.S. Patent 4,303,556 issued December 1, 1981.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates having the formula: wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to 0.5:1, and X is an integer from 15 to 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least 2 grainsl minutelgram.
  • a preferred material is Zeolite A which is:
  • the level of detergency builder of the bleaching compositions is from 0% to about 70%, preferably from 10% to 60% and most preferably from 20% to 60%.
  • Buffering agents can be utilized to maintain the desired alkaline pH of the bleaching solutions.
  • Buffering agents include, but are not limited to many of the detergency builder compounds disclosed hereinbefore.
  • Buffering agents suitable for use herein are those well known in the detergency art.
  • Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
  • U.S. Patents 3,933,672, issued January 20, 1976 to Bartolotta et al, and 4,136,045, issued January 23, 1979 to Gault et al disclose silicone suds controlling agents.
  • Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S. Patent 4,073,118, Gault et al, issued February 21, 1978.
  • An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • Suds modifiers as described above are used at levels of up to approximately 2%, preferably from 0.1 1 to 11% by weight of the surfactant.
  • Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of preferred suds control components for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977,
  • microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
  • Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 25 ° C by ASTM-D1321.
  • Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petroleum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; cande- lilla; and carnauba wax.
  • Alkyl phosphate esters represent an additional preferred suds control agent for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphate, which can contain di- and trioleyl phosphate.
  • suds control agents useful in the practice of the invention are the soap or the soap and nonionic mixtures as disclosed in U.S. Patents 2,954,347 and 2,954,348,
  • Fluorescent or optical brighteners can be utilized within the bleaching compositions of the invention. Surprisingly, such brighteners exhibit acceptable compatibility with such compositions. Suitable anionic brighteners are disclosed in U.S. Patents 3,537,993 Coward et al (November 3, 1970) and 3,953,380 Sundby (April 27, 1976). Nonionic brighteners can also be utilized within the compositions of the invention.
  • a laundry load consisting of one set of the six swatches, four clean terry cloth towels and one terry cloth towel soiled with 1.5 grams of a mixture of artificial body soil and vacuum cleaner soil was placed in a mini-wash system. This laundry load was then washed with 8.5 grams of the above granular detergent composition in 5.5 liters of water. This mini-wash system with such a load and granular detergent concentration simulates a conventional automatic wash process.
  • the wash water temperature was 37°C and the wash water contained - 136 pp m water hardness.
  • the initial pH of the wash water was about 9.7.
  • each of the swatches was visually graded by comparing it to its unwashed counterpart. A grading scale of 0 to 5 was used, with 0 indicating no stain removal and 5 indicating 100% stain removal. Each swatch was graded by three graders and then the average grade for each swatch was calculated. This average was then scaled from 0 to 100, with 100 being 100% stain removal. Also, the mean for the set of swatches was calculated.
  • Bleaching systems 5-7 and 9 which are within the compositions of the invention, provided significantly more stain removal and, therefore, surface bleaching than bleaching systems 2-4 and 8 which are outside the compositions of the invention because they did not contain an aromatic sulfonyl halide bleach activator.
  • Bleaching system 2 contained neither a peroxycarboxylic acid source nor an aromatic sulfonyl halide bleach activator.
  • Bleaching system 3 did not contain a peroxycarboxylic acid source and bleaching systems 4, 6 and 8 did not contain an aromatic sulfonyl halide bleach activator.
  • Bleaching system 3 which is within the compositions of the invention, provided significantly more surface bleaching than bleaching composition 2, which is without the compositions of the invention because it did not contain an aromatic sulfonyl halide bleach activator. Also, it should be noted that since the pK of m-chloroperoxybenzoic acid is 7.57, the pH of the wash water was optimum for bleaching performance of the m-chloroperoxybenzoic acid alone.
  • a quantity of m-chloroperoxybenzoic acid was added to the solution to give a 1.25 x 10 -4 molar concentration.
  • the percent transmittance (T) was measured with a Brinkman Colorimeter Model PC700 equipped with a 440 nm filter. This measurement indicates the amount of methylene blue dye that is destroyed in the solution; a higher change in percent T indicates a larger amount of dye that is destroyed.
  • a quantity of 1,3-benzenedisulfonyl chloride was added to the solution to give a 6.25 x 10 -5 molar concentration, which is an equivalent amount to the m-chloroperoxybenzoic acid.
  • the percent T was measured after 30 seconds. This entire procedure was repeated but benzoyl peroxide was substituted for the m-chloroperoxybenzoic acid. The results were as follows:
  • 1,3-benzenedisulfonyl chloride to either m-chloroperoxybenzoic acid or benzoyl peroxide, which are compositions within the invention, rapidly increases the destruction of the methylene blue dye as compared to the m-chloroperoxybenzoic acid alone, which is without the compositions of the invention. It is believed that increased methylene blue dye destruction corresponds to increased solution bleaching efficacy on soils.
  • ⁇ E is a measurement of the change in color of the swatch resulting from the treatment in the tergotometer. The greater the ⁇ E value, the greater the change in color, It is believed that a larger ⁇ E value for the dyed swatches represents better surface bleaching performance and a smaller AE value for the undyed swatches represents better solution bleaching.
  • Bleaching systems 2-5, 7 and 11 which are within the compositions of the invention, provided significantly more surface bleaching and solution bleaching than was obtained with bleaching systems 1,6, and 8-10, which are without the compositions of the invention because they did not contain an aromatic sulfonyl halide bleach activator.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP19830305726 1982-09-30 1983-09-26 Compositions de blanchiment Expired EP0105690B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83305726T ATE35691T1 (de) 1982-09-30 1983-09-26 Bleichmittelzusammensetzungen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US43056282A 1982-09-30 1982-09-30
US53245683A 1983-09-16 1983-09-16
US532456 1983-09-16
US430562 1995-04-28

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EP0105690A1 true EP0105690A1 (fr) 1984-04-18
EP0105690B1 EP0105690B1 (fr) 1988-07-13

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EP (1) EP0105690B1 (fr)
CA (1) CA1207955A (fr)
DE (1) DE3377361D1 (fr)
GR (1) GR81268B (fr)
IE (1) IE55976B1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0137669A1 (fr) * 1983-08-27 1985-04-17 The Procter & Gamble Company Compositions détergentes
EP0195663A2 (fr) * 1985-03-20 1986-09-24 The Procter & Gamble Company Compositions pour le blanchiment
EP0267175A2 (fr) * 1986-11-03 1988-05-11 Monsanto Company Acides peroxycarboxyliques sulfoniques
US4758369A (en) * 1986-11-03 1988-07-19 Monsanto Company Sulfone peroxycarboxylic acids
US4824591A (en) * 1987-09-17 1989-04-25 Monsanto Company Sulfone peroxycarboxylic acids
EP0337535A2 (fr) * 1988-04-14 1989-10-18 Unilever N.V. Composition de blanchiment
JPH0317197A (ja) * 1989-05-10 1991-01-25 Unilever Nv 漂白活性化及び漂白組成物
US5004558A (en) * 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
EP3266762A1 (fr) 2016-07-06 2018-01-10 3V SIGMA S.p.A Activateurs pour composés peroxygénés

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10280386B2 (en) 2015-04-03 2019-05-07 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US10870818B2 (en) 2018-06-15 2020-12-22 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2737865A1 (de) * 1976-08-27 1978-03-02 Procter & Gamble Peroxysaeure-bleichmittel mit verbesserter regulierung exothermer reaktionen
US4107065A (en) * 1975-11-05 1978-08-15 Colgate-Palmolive Company Activated peroxy compound bleaching compositions and bleaching detergent compositions
US4292191A (en) * 1975-11-05 1981-09-29 Colgate-Palmolive Company Activated peroxy compound bleaching compositions and bleaching detergent compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4107065A (en) * 1975-11-05 1978-08-15 Colgate-Palmolive Company Activated peroxy compound bleaching compositions and bleaching detergent compositions
US4292191A (en) * 1975-11-05 1981-09-29 Colgate-Palmolive Company Activated peroxy compound bleaching compositions and bleaching detergent compositions
DE2737865A1 (de) * 1976-08-27 1978-03-02 Procter & Gamble Peroxysaeure-bleichmittel mit verbesserter regulierung exothermer reaktionen

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0137669A1 (fr) * 1983-08-27 1985-04-17 The Procter & Gamble Company Compositions détergentes
EP0195663A2 (fr) * 1985-03-20 1986-09-24 The Procter & Gamble Company Compositions pour le blanchiment
EP0195663A3 (fr) * 1985-03-20 1987-05-13 The Procter & Gamble Company Compositions pour le blanchiment
US5004558A (en) * 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
EP0267175A2 (fr) * 1986-11-03 1988-05-11 Monsanto Company Acides peroxycarboxyliques sulfoniques
US4758369A (en) * 1986-11-03 1988-07-19 Monsanto Company Sulfone peroxycarboxylic acids
EP0267175A3 (en) * 1986-11-03 1989-03-01 Monsanto Company Sulfone peroxycarboxylic acids
US4824591A (en) * 1987-09-17 1989-04-25 Monsanto Company Sulfone peroxycarboxylic acids
EP0337535A3 (fr) * 1988-04-14 1990-09-19 Unilever N.V. Composition de blanchiment
EP0337535A2 (fr) * 1988-04-14 1989-10-18 Unilever N.V. Composition de blanchiment
AU615531B2 (en) * 1988-04-14 1991-10-03 Unilever Plc Bleaching composition
JPH0317197A (ja) * 1989-05-10 1991-01-25 Unilever Nv 漂白活性化及び漂白組成物
US5106528A (en) * 1989-05-10 1992-04-21 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation and bleaching compositions
EP3266762A1 (fr) 2016-07-06 2018-01-10 3V SIGMA S.p.A Activateurs pour composés peroxygénés

Also Published As

Publication number Publication date
DE3377361D1 (en) 1988-08-18
IE55976B1 (en) 1991-03-13
GR81268B (fr) 1984-12-11
IE832298L (en) 1984-03-30
CA1207955A (fr) 1986-07-22
EP0105690B1 (fr) 1988-07-13

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