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
  • C11D3/3907—Organic compounds

Definitions

• Thls invention relates to granular detergent-bleaching compositions. More particularly, this invention relates to detergent-bleaching compositions that provide effective and efficient surface bleaching of soils in laundry processes over a wide range of bleach solution temperatures without excessive damage to dyed fabrics.
• the detergent-bleaching compositions within the invention contain peroxygen bleaches capable of yielding hydrogen peroxide in aqueous solutions and specific bleach activators. This invention also relates to mixtures of activators that are especially useful in such compositions
• 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.
• bleach solution temperatures of 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.
• peroxygen bleaches are rendered ineffective, regardless of the level of peroxygen bleach added to the system.
• 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 present invention comprises a granular detergent-bleaching composition comprising:
• This invention relates to granular solid detergent-bleaching compositions containing peroxygen bleaches capable of yielding hydrogen peroxide in an aqueous solution and specific bleach activators, hereinafter defined, at specific molar ratios of hydrogen peroxide to bleach activator.
• Such compositions provide extremely effective and efficient detergency and surface bleaching.
• the compositions are particularly effective when used to remove 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 or yellow tint. These soils tend to be a blend of particulate and greasy materials. The removal of this type of soil is sometimes referred to as "dingy fabric clean up".
• the detergent-bleaching compositions of this invention provide such bleaching over a wide range of bleach solution temperatures. Such bleaching is obtained in detergent-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.
• activators containing C 10 acyl groups provide a remarkably safe solid detergent-bleach composition that gives significantly less damage to bleach sensitive dyes, even under stressed conditions than does the corresponding C 8 or Cg acyl group.
• the molar ratio of hydrogen peroxide yielded by the peroxygen bleach to bleach activator is at least about 1.
• the molar ratio should be greater than about 1.5 and preferably at least about 2.0.
• increasing such molar ratio above 1.5 results in not only faster formation of the percarboxylic acid, but, most importantly, more percarboxylic acid being formed.
• the activator may hydrolyze to carboxylic acid before it perhydrolyzes.
• the percarboxylic acid that is formed can further react with the unreacted bleach activator to form a diacyl peroxide. Consequently, lower concentrations of percarboxylic acid are ultimately achieved and, therefore, bleaching performance is lowered.
• Such competing chemical reactions are minimized by the addition of more peroxygen bleach. Accordingly, bleaching performance is enhanced, especially for dingy fabrics.
• ratio can generally be expressed as the molar ratio of peroxygen bleach to bleach activator because the vast majority of peroxygen bleaches yield one mole of hydrogen peroxide per mole of peroxygen bleach.
• One mole of bleach activator is equal to one acyl group which can undergo perhydrolysis to form a peroxyacid.
• Optimum bleaching performance is obtained with detergent-bleaching solutions wherein the initial pH of such solution is between about 8.5 and 10.5 and preferably between 9 and 10.3. It is preferred that such pH be greater than 9 to optimize the perhydrolysis reaction and thus surface bleaching performance, and also to help prevent the bleaching solution from having an undesirable odor.
• the solution odor of C 10 acyl activator is better than that of C 8 or Cg acyl activators when they are used alone. With the preferred mixtures of activators, the solution odor is also much less noticeable.
• Such pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching compositions herein.
• the peroxygen bleaching compounds useful herein are those capable of yielding hydrogen peroxide in an aqueous solution. 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- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution. It is believed that such rapid dissolution results in the formation of higher levels of peroxycarboxytic acid and, thus, enhanced surface bleaching performance.
• the level of peroxygen bleach within compositions of the invention is from about .1% to about 60% and preferably from about 1% to about 20%.
• the bleach activators within the invention have the general formula: wherein R is an alkyl group containing 9 carbon atoms in at least about 10% of the activator, the remainder of the alkyl groups containing from about 7 to about 10 carbon atoms, and L is a leaving group, the conjugate acid of which has a pK a in the range of from about 6 to about 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, the perhydrolysis reaction, results in the formation of the peroxycarboxylic acid.
• a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion.
• Leaving groups that exhibit such behavior are those in which their conjugate acid has a pK a in the range of from about 6 to about 13, preferably from about 7 to about 11 and most preferably from about 8 to about 11.
• Preferred bleach activators are those of the above general formula wherein L is selected from the group consisting of: and mixtures thereof and wherein R is as defined in the general formula, R 2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R 3 is H or R 2 , and Y is H or a solubilizing group.
• the preferred solubilizing groups are -COO - M + , (-N + R 3 4 )X - and -NR24+O and most preferably and -COO - M + wherein R 4 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 a halide, hydroxide, methylsulfate or acetate anion.
• the bleach activators preferably have a leaving group that contains a solubilizing group in order to assist in their dissolution.
• Preferred bleach activators are those of the above general formula wherein R is a mixture of linear alkyl chains.
• the preferred bleach activators contain R groups which are linear alkyl chains of which from about 10% to about 90% contain 9 carbon atoms, more preferably from about 20% to about 80%, and L is selected from the group consisting of: and mixtures thereof wherein R, R2, R 3 and Y are as defined above.
• the activator Preferably less than about 70%, most preferably less than about 50% of the activator contains any single acyl group, for odor reasons.
• Particularly preferred bleach activators are those of the above preferred formulas wherein L is selected from the group consistina of: and mixtures thereof wherein R 2 is as defined above and Y is -SO 3 - M + or -COO - M + wherein M is as defined above.
• the most preferred bleach activators have the formula: wherein R is a mixture of linear alkyl chain containing from about 7 to about 10 carbon atoms of which at least about 10% contain 9 carbon atoms, and M is sodium or potassium.
• Particularly preferred are 60140 mixtures of C8 and C10 acyl chains alone and in combination with a C 9 acyl chain. Mixtures of C 9 and C 10 acyl groups are even more preferred.
• These mixtures preferably have the leaving groups L which are indicated as being preferred hereinbefore, and have linear alkyl chain R groups. Such mixtures have surprisingly better odor characteristics.
• the level of bleach activator within the compositions of the invention is from about .1% to about 40%, preferably from about .5% to about 20%, most preferably from about 1% to about 5%.
• the solid detergent-bleaching compositions of the invention contain detergent surfactant.
• the detergent surfactant 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, both incorporated herein by reference.
• 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, both incorporated herein by reference.
• the following are representative examples of detergent surfactants useful in the present compositions.
• 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 alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an 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 (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
• 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 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 about 1 to about 10 units 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, preferably from about 1 to about 3, units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20, preferably from about 14 to about 16, carbon atoms.
• Other useful anionic surfactants herein 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-1-sutfonic 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; 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.
• Water-soluble nonionic surfactants are also useful in the compositions of the 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.
• 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 3 to 12 moles of ethylene oxide per mole of alcohol.
• Particularly preferred are the condensation products of alcohots having an alkyl group containing from about 9 to 15 carbon atoms with from about 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 about 10 to 18 carbon atoms and -two moieties selected from the group of alkyl and hydroxyatkyt 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.
• 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.
• the level of detergent surfactant that is employed is from about 1% to about 50%, preferably from about 5% to about 30% and most preferably from about 10% to about 25% by weight of the total composition.
• detergency builder can be employed in the granular bleaching compositions.
• Water-soluble inorganic or organic electrolytes are suitable builders.
• the builder can also be water-insoluble calcium ion exchange materials.
• 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 aminopolyace- tates, for example, nitrilotriacetates, glycinates, ethylenediamine- tetraacetates, N-(2-hydroxyethyl)nitrilodiacetates and diethyl- enetriaminepentaacetates; (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 ethylenediphosphonic 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-
• 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 Belgian Patent 814,874, issued November 12, 1974, incorporated herein by reference.
• 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 about 0.5:1, and X is an integer from about 15 to about 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 about 2 grains/gallon/minute/gram.
• 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 about 10% to about 60%, and most preferably from about 20% to about 60%.
• 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, incorporated herein by reference.
• 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.
• Buffering agents can be utilized to maintain the desired alkaline pH of the detergent-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.
• silicone suds controlling agents can be represented by alkylated polysiloxane materials such as silica aerogels and xero- gels and hydrophobic silicas of various types.
• the silicone material can be described as siloxane havina the formula: wherein x is from about 20 to about 2,000 and R and R are each alkyl or aryl groups, especially methyl; ethyl, propyl, butyl and phenyl.
• the polydimethylsiloxanes (R and R are methyl) having a molecular weight within the range of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agents.
• Additional suitable silicone materials wherein the side chain groups R and R are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpolysiloxanes and the like.
• Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
• a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m 2 /gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2.
• the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
• 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, incorporated herein by reference.
• 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 about 0.1 to about by weight of detergent 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, incorporated herein by reference.
• the 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 77°F 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, incorporated herein by reference.
• Fabrics are prepared by splitting dirty, dingy T-shirts, pillowcases, and dish towels into swatches. Terry cloth towels are preconditioned with artificial body soils so as to simulate household laundry. Other fabric swatches were stained with six different bleachable stains.
• Each laundry load consists of five terry cloth towels, nine dingy swatches (3 each from T-shirts, pillow cases, and towels), and six different stained swatches.
• the laundry loads are washed in the mini-wash system with a quantity of the above detergent composition that corresponds to 1250 ppm in the wash water (which is typical of conventional automatic wash processes) and, as required, a bleach system containing sodium perborate monohydrate and a sodium fatty acyloxybenzene sulfonate.
• the mini-wash system with such a load simulates a conventional automatic wash process.
• the wash water temperature was 37°C. and the rinse water temperature was 22°C. and both contained 2 gallons of water with 5 grains/gallon hardness.
• the detergent composition was one treatment and three additional treatments contained the detergent composition and 1:1 mixtures of sodium perborate monohydrate and sodium C 8 fatty acyloxybenzene sulfonate (bleach activator) at total concentrations of 90, 180, and 270 ppm respectively for the perborate/bleach activator mixture.
• the detergent composition was one treatment and in three additional treatments the detergent composition and mixtures of sodium perborate and sodium C 10 acyloxybenzene sulfonate were used, the level of sodium perborate monohydrate being the same as in the first series of tests and the sodium C 10 acyloxybenzene sulfonate being substituted for the sodium C 8 acyloxybenzene sulfonate of the first series on an equal molar basis.
• Each of the dingy swatches was then comparison graded with its original other half to determine relative stain removal.
• a grading scale of -4 to 4 was used, with -4 indicating much less stain removal, 0 indicating no difference and 4 indicating much more stain removal.
• the average of the grades for each fabric of each mini-wash system was calculated.
• the swatches that are felt to most accurately reflect bleach performance are dingy T-shirts, pillow cases (PC), and dish towels (DT). These swatches were graded against the product with no bleach present. These paired comparisons were as follows:
• decanoyloxybenzene sulfonate is better, or at least equal to the octanoyloxybenzene sulfonate.
• the granular detergent compositions herein had the general formula:
• the different fabric swatches for each treatment were placed at the bottom of a Kenmore top loading automatic washer and then covered with 5.5 pounds of clean ballast items.
• City and soft water about 6 grains of calcium and magnesium hardness total
• the water temperature was 95°F.
• Each treatment consisted of a granular detergent as de - scribed above.
• the acyl groups for the sodium fatty acyloxybenzene sutfonate were 100% heptanoyl (C 7 ) , octanoyl (C 8 ), nonanoyl (C 9 ) or decanoyl (C 10 ). Each experiment was replicated twice.
• the colored swatches were round robin graded against each other using a grading scale of -4 to 4 with -4 indicating much more color fading, 0 indicating no difference, and 4 indicating much less color fading.
• the decanoyl (C 10 ) variation surprisingly provides less color fading than the lower chain lengths.
• Treatment A the product contained 9% perborate and 3% C 8 acyloxybenzene sulfonate; in Treatment B, the product contained 3.5% perborate and 3% C 9 acyloxybenzene sulfonate; and in treatment C, the product contained 3.5% perborate and 3.0% C 10 acyloxybenzene sulfonate.
• the solutions gave the following odor results.
• A's solution had a strong odor which was characterized as a sour, acidic, bleach off-odor.
• B's solution had a strong odor which was characterized as a rancid, fatty, bleach off-odor.

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