JPS6312520B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to bleaching compositions. More specifically,
The present invention relates to bleaching compositions that provide effective and efficient surface bleaching of fabrics over a wide range of bleach temperatures. Surface bleaching of fabrics is a bleaching in which the bleaching mechanism occurs on the fabric surface thereby removing stains and/or soils. The bleaching compositions of the present invention contain a peroxygen bleaching agent capable of producing hydrogen peroxide in an aqueous solution and a specific bleach activator in a specific molar ratio of hydrogen peroxide to bleach activator. In a highly preferred embodiment, the bleaching composition of the present invention is a cleaning composition. Although peroxygen bleaches have long been known to be effective in removing stains and/or soils from fabrics, they have also long been known to be highly temperature dependent. Bleaches of this type are essentially practical and/or effective only in bleach solutions, ie, mixtures of bleach and water, whose temperature is above about 60°C. At bleach solution temperatures of approximately 60°C, peroxygen bleach is only partially effective and therefore very large amounts of peroxygen bleach must be added to the system to obtain the desired level of bleaching performance. Must be.
This is economically unfeasible. bleach solution temperature
Once the temperature drops below 60°C, peroxygen bleach is no longer effective, regardless of the amount of peroxygen bleach added to the system. The temperature dependence of peroxygen bleaches is important because this type of bleach is commonly used as a detergent adjunct in fabric washing processes utilizing automatic domestic washing machines with wash water temperatures below 60°C. This type of washing temperature is utilized due to the care and energy considerations of the fabric. As a result of this type of cleaning method, there has been much industrial research to develop substances commonly referred to as bleach activators that make peroxygen bleaches effective at bleach temperatures below 60°C. A number of materials have been disclosed in the art as effective bleach activators. Background Art Carboxylic acid ester bleach activators are known. British Patent No. 864798 describes the use of inorganic persalts and organic esters of aliphatic carboxylic acids (the carboxylic acid ester particles are of a size such that at least 70% are retained on a 60 mesh British standard sieve). ) is disclosed. Preferably, the ester is derived from an aliphatic carboxylic acid having up to 10 carbon atoms, preferably less than 8 carbon atoms.
The ratio of molecules of reactive ester to each atom of available oxygen in the persalt is from 1/4 to 4, preferably from 1/2 to 1.5. Bleaching compositions of this type are described as being stable on storage. GB 836988 discloses bleaching compositions containing hydrogen peroxide or an inorganic persalt salt and an organic carboxylic acid ester. Tests defining the esters of the invention are described. The number of ester molecules per available oxygen atom is from 1/4 to 2, in particular from 1/2 to 1.5. Esters of this type are said to give improved bleaching at temperatures of 50 DEG C. to 60 DEG C. compared to those obtained with persalts alone. It is also known that bleach activators, which are believed to exhibit surface activity and are used in conjunction with peroxygen bleaches, provide particularly effective surface bleaching. U.S. Pat. No. 4,283,301 discloses peroxygen bleach and the general formula

[Formula] Ma Taha

[Formula] [wherein R is an alkyl chain having about 5 to about 13 carbon atoms, R ² is an alkyl chain having about 4 to about 24 carbon atoms, and each Z is a leaving ( A bleaching composition comprising a bleach activator of the following type is disclosed. Preferably, such bleach and bleach activator are present in equimolar ratios. SUMMARY OF THE INVENTION The present invention is capable of producing hydrogen peroxide in aqueous solution selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate peroxide, and mixtures thereof. peroxygen bleaching compound, and (b) general formula (wherein R is an alkyl group having about 5 to about 18 carbon atoms, and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms, and M is a cation that confers solubility to the bleach activator), and the molar ratio of hydrogen peroxide produced by (a) to bleach activator (b) is approximately The present invention provides a bleaching composition characterized in that the bleaching composition is greater than 1.5. DETAILED DESCRIPTION OF THE INVENTION The present invention provides bleach compositions containing peroxygen bleaches capable of producing hydrogen peroxide in an aqueous solution and certain bleach activators as described below in certain molar ratios of hydrogen peroxide to bleach activators. relating to things. Compositions of this type provide highly effective and efficient surface bleaching of fabrics,
Stains and/or soils are thereby removed from the fabric. The composition is particularly effective in removing sooty stains from fabrics. Sooty stains are stains that build up on fabrics after numerous cycles of use and cleaning, giving white fabrics a gray tint. These soils tend to be a combination of particulates and greasy substances. This type of soil removal is sometimes referred to as "sooty fabric cleaning." The bleaching compositions of the present invention provide this type of bleaching over a wide range of bleach solution temperatures. This type of bleaching is obtained in a bleaching solution whose temperature is at least about 5°C. Without a bleach activator, this type of peroxygen bleach would be ineffective and/or inoperable at temperatures below about 60°C. The bleaching compositions of the present invention are extremely efficient. To achieve the same level of surface bleaching performance obtained with similar bleach activators having only about 2 to about 5 carbon atoms in the longest linear alkyl chain extending from and encompassing the carbonyl carbon. Additionally, on a molar basis, the present invention requires significantly less of the bleach activator of the present invention. Without being limited by theory, it is believed that this type of efficiency is achieved because the bleach activators of the present invention exhibit surface activity. This can be explained as follows. Bleaching mechanisms in general and surface bleaching mechanisms in particular are not completely understood. However, it is generally believed that bleach activators produce percarboxylic acids upon nucleophilic attack by perhydroxide anions generated from hydrogen peroxide generated by peroxygen bleaches.
This reaction is commonly called perhydrolysis. The percarboxylic acid then forms a reactive dimer with its anion, which generates singlet oxygen, which is believed to be the reactive bleaching component. It is theorized that singlet oxygen must be generated at or near the fabric surface to provide surface bleaching. Otherwise, singlet oxygen will provide bleaching, but not on the fabric surface. This type of bleaching is known as solution bleaching, ie bleaching the soil in a bleach solution. In order to ensure that singlet oxygen is generated more efficiently at the fabric surface, the longest linear alkyl chain extending from and including the carbonyl carbon of the percarboxylic acid has from about 6 to about 6 carbon atoms.
It is mandatory to have 10. This type of percarboxylic acid is surface active and therefore tends to concentrate on the surface of fabrics. Percarboxylic acids of this type with fewer carbons in the alkyl chain have similar redox potentials but do not have the ability to concentrate on fabric surfaces. Therefore,
The bleach activators of this invention provide the same level of surface bleaching performance on a molar basis as similar bleach activators outside the scope of this invention having fewer carbons in the alkyl chain of this type. , it is extremely efficient as only a fairly small amount of bleach activator is required. Based on the same theory described above, the bleach activator of the present invention is capable of inhibiting peroxygen bleach even at bleach solution temperatures at which the bleach activator is not required to activate the bleach, i.e., above about 60°C. It is also conceivable that it can be made even more efficient. Therefore, with the bleach compositions of the present invention, less peroxygen bleach is required to obtain the same level of surface bleaching performance as would be obtained with peroxygen bleach alone. The molar ratio of hydrogen peroxide to bleach activator produced by a peroxygen bleach is critical to obtaining the desired level of surface bleaching performance. To obtain this type of performance, it is essential that the molar ratio be greater than about 1.5, and preferably at least about 2.0.
Surprisingly, increasing the molar ratio above 1.5 not only produces percarboxylic acid more rapidly, but most importantly, a larger amount of percarboxylic acid is produced. For molar ratios of such components below about 1.5, there is primarily competitive chemical reaction occurring.
The percarboxylic acid produced further reacts with unreacted bleach activator to form diacyl peroxide. This type of competitive chemical reaction is believed to occur primarily due to hydrophobic-hydrophobic interactions between the alkyl chain of the acyl group of the percarboxylic acid and unreacted bleach activator. Therefore, a lower concentration of percarboxylic acid is finally achieved and therefore the bleaching performance is very poor. This type of competitive chemical reaction is minimized by adding more peroxygen bleach. Therefore, surface bleaching performance is enhanced especially for sooty fabrics. The longest linear alkyl chain extending from and encompassing the carbonyl carbon is shorter (i.e.
C _2-5 ) or longer (i.e. C ₁₁ or more), so
Bleach activators that are similar to the bleach activators of this invention but outside the scope of this invention increase the molar ratio of hydrogen peroxide to bleach activator produced by peroxygen bleaches to 1.5 or more. It does not produce significantly more percarboxylic acid during expansion. For this type of bleach activator with shorter alkyl chains, experimental evidence shows that the molar ratio of hydrogen peroxide to bleach activator produced by peroxygen bleaches of 1 is essentially the theoretical maximum. This indicates that percarboxylic acid is produced, ie, that the percarboxylic acid produced does not react further with unreacted bleach activator. Therefore, adding more peroxygen bleach will not provide additional percarboxylic acid. Experimental evidence in the case of bleach activators of this type with longer alkyl chains shows that, despite the addition of very high peroxygen bleach, only insignificant amounts of percarboxylic acid are formed at the end. show. Bleach activators of this type are so hydrophobic that it is believed that regardless of the amount of peroxygen bleach, primarily percarboxylic acids react with unreacted bleach activator to form diacyl peroxides. Only the bleach activators of this invention are advantageously influenced by the molar ratio of hydrogen peroxide to bleach activator produced by peroxygen bleaches greater than about 1.5. There is essentially no upper limit to this type of molar ratio since addition of more peroxygen bleach is not detrimental to the system.
However, at ratios greater than about 10, essentially all of the stoichiometric amount of percarboxylic acid that can be produced is produced. Adding more peroxygen bleach is not economically practical or desirable. However, more peroxygen bleach can be added and provides additional benefits when bleaching at bleach solution temperatures where the bleach activator is not required to activate the peroxygen bleach, ie, 60° C. or higher. This means "boiling water"
This is especially true under European cleaning conditions that utilize It is also common for European detergent compositions to contain extremely high amounts of peroxygen bleach.
Based on this, the upper limit for the molar ratio of hydrogen peroxide to bleach activator produced by a peroxygen bleach is about 500. Since most peroxygen bleaches produce 1 mole of hydrogen peroxide per mole of peroxygen bleach, this type of ratio is commonly expressed as the molar ratio of peroxygen bleach to bleach activator. It should be kept in mind. Optimal surface bleaching performance is achieved when the pH of the bleaching solution is approximately 8.5 ~
10.5, preferably 9-10. The PH is preferably higher than 9, not only to optimize surface bleaching performance, but also to prevent the bleaching solution from having undesirable odors. It has been observed that when the pH of the bleach solution drops below 9, the bleach solution begins to have an undesirable odor. This type of PH is obtained using substances commonly known as buffering agents, which are optional components of the bleaching compositions of the present invention. The following is a specific description of the essential and optional ingredients of the bleaching composition of the present invention. All percentages, parts and ratios are by weight unless otherwise specified. Peroxygen Bleaching Compounds Peroxygen bleaching compounds useful in the present invention are those that are capable of producing hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include, for example, hydrogen peroxide and alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds such as alkali metal perborates. salts, percarbonates, superphosphates, etc. If desired, mixtures of two or more such bleaching compounds can also be used. The peroxygen bleaching compounds used in the present invention include sodium perborate, sodium carbonate peroxide, commercially available in monohydrate and tetrahydrate forms;
and mixtures thereof. Particular preference is given to sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is particularly preferred because it is very stable on storage and still dissolves very quickly in bleach solutions. It is believed that such rapid dissolution produces large amounts of percarboxylic acid and therefore enhances surface bleaching performance. The amount of peroxygen bleach in the compositions of the present invention is approximately
0.1% to about 95%, preferably about 1% to about 60%. When the bleaching composition of the present invention is also a detergent composition, the amount of peroxygen bleach is preferably from about 1% to about 20%. Bleach Activator The bleach activator of the present invention has the general formula (wherein R is an alkyl group having about 5 to about 18 carbon atoms, and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms; and M is a cation that confers solubility to the active agent). Preferably M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred. Particularly preferred bleach activators include R having 5 to 5 carbon atoms;
12 and the longest linear portion of the alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms. Particularly preferred bleach activators have R of about 5 carbon atoms.
to about 9, preferably about 6 to about 8 linear alkyl chains. The most preferred bleach activator has the formula where R is a linear alkyl chain having about 5 to about 9 carbon atoms, preferably about 6 to about 8 carbon atoms, and M is sodium or potassium. The amount of bleach activator in the compositions of the present invention is approximately
0.1% to about 60%, preferably about 0.5% to about 40%. When the bleach composition of the present invention is also a detergent composition, the amount of bleach activator is preferably from about 0.5% to about 20%. Optional Ingredients In a preferred embodiment, the bleaching composition of the present invention can be a detergent composition. Thus, the bleaching composition can contain typical detergent composition ingredients such as detergent surfactants and detergency builders. In preferred embodiments of this type, bleaching compositions are particularly effective. The bleaching compositions of the present invention contain all the usual ingredients of detergent compositions, such as U.S. Pat.
It can contain the components described in No. 3936537. Ingredients of this type are, for example, color speckles, foam enhancers, foam inhibitors, corrosion inhibitors and/or corrosion inhibitors, soil suspending agents,
Stain release agents, dyes, fillers, optical brighteners, disinfectants, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizers, fragrances, etc. The detergent surfactant is one type of surfactant selected from anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and compatible mixtures thereof. It can be more than that. Detergent surfactants useful in the present invention include:
U.S. Patent No. 3,664,961 and U.S. Pat.
It is described in the specification of No. 3919678. Useful cationic surfactants are, for example, those described in US Pat. No. 4,222,905 and US Pat. No. 4,239,659. The following are representative examples of detergent surfactants useful in the present compositions. Water-soluble salts of higher fatty acids, or "soaps", are useful anionic surfactants in the present compositions. These are alkali metal soaps such as sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be produced by direct saponification of fats and oils and by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, ie, sodium or potassium tallow soaps and coconut soaps. Also useful anionic surfactants are, for example, water-soluble salts of organic sulfuric acid reaction products having an alkyl group of about 10 to about 20 carbon atoms and a sulfonic acid ester group or a sulfuric acid ester group in their molecular structure, preferably are alkali metal salts, ammonium salts and alkylol ammonium salts (“alkyl”
(includes the alkyl portion of an acyl group). Examples of this group of synthetic surfactants are sodium alkyl sulfates and potassium alkyl sulfates, especially higher alcohols (C ₈ -
and _sodium alkylbenzenesulfonates and potassium alkylbenzenesulfonates in which the alkyl group has from about 9 to about 15 carbon atoms in a straight-chain or branched configuration; For example, of the type described in US Pat. Nos. 2,220,099 and 2,477,383. The average number of carbon atoms in the alkyl group is approximately 11~
Of particular value are the linear straight-chain alkylbenzene sulfonates (abbreviated _C11-13 LAS) which are 13. Other anionic surfactants are sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonate and sodium coconut oil fatty acid monoglyceride sulfate; 1 molecule Sodium or potassium salts of alkylphenol ethylene oxide ether sulfuric acid containing about 1 to about 10 units of ethylene oxide per molecule and having an alkyl group of about 8 to about 12 carbon atoms; and about 1 to about 10 units of ethylene oxide per molecule; Contains and has an alkyl group with approximately carbon number
10 to about 20 alkyl ethylene oxide ether sulfuric acid salts. Other anionic surfactants useful in the present invention include, for example, water-soluble esters of α-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group. 2-acyloxyalkane having about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety;
Water-soluble salts of 1-sulfonic acids; water-soluble salts of olefinsulfonic acids and paraffinsulfonic acids having about 12 to 20 carbon atoms; and water-soluble salts of olefinsulfonic acids and paraffinsulfonic acids having about 12 to 20 carbon atoms; and Approximately 8
-20. Water-soluble nonionic surfactants are also useful in the compositions of the present invention. Nonionic substances of this type are, for example, compounds formed by condensation of an alkylene oxide group (hydrophilic) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic. The length of the polyoxyalkylene group that is fused with a particular hydrophobic group can be easily adjusted to produce a water-soluble compound with the desired balance between hydrophilic and hydrophobic elements. Suitable nonionic surfactants are, for example, polyoxyethylene oxide condensates of alkylphenols, such as alkylphenols with alkyl groups having about 6 to 15 carbon atoms in either a linear or branched configuration and 1 mol of alkylphenols. It is a condensate with about 3 to 12 moles of ethylene oxide per ethylene oxide. Preferred nonionic surfactants are water-soluble and water-dispersible condensates of aliphatic alcohols having from 8 to 22 carbon atoms in either a linear or branched configuration with 3 to 12 moles of ethylene oxide per mole of alcohol. It is. Particularly preferred are condensates of alcohols with alkyl groups having about 9 to 15 carbon atoms and about 4 to 8 moles of ethylene oxide per mole of alcohol. Semipolar nonionic surfactants, for example, have a carbon number of approx.
A water-soluble amine oxide containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group of alkyl moieties of about 1 to about 3 carbon atoms and hydroxyalkyl moieties; 1 alkyl moiety of about 10 to 18 carbon atoms
a water-soluble phosphine oxide containing two moieties selected from the group consisting of an alkyl group having about 1 to 3 carbon atoms and a hydroxyalkyl group; and one alkyl moiety having about 10 to 18 carbon atoms and a carbon number A water soluble sulfoxide containing about 1 to 3 alkyl moieties and one moiety selected from the group consisting of hydroxyalkyl moieties. Amphoteric surfactants can be used, for example, in which the aliphatic moiety can be linear or branched and one of the aliphatic substituents has about 8 to 18 carbon atoms and at least one aliphatic substituent is anionic. Derivatives of aliphatic secondary and tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines containing ionic water-solubilizing groups. Zwitterionic surfactants are, for example, derivatives of aliphatic quaternary ammonium compounds, phosphonium compounds and sulfonium compounds in which one of the aliphatic substituents has about 8 to 18 carbon atoms. The amount of detergent surfactant that can be used is from 0 to about 50%, preferably from about 1 to about 30%, by weight of the total composition;
Most preferably from about 10 to about 25% by weight. In addition to detergent surfactants, detergency builders can be used in bleaching compositions. Water-soluble inorganic or organic electrolytes are suitable builders. The builder can also be a water-insoluble calcium ion exchange material. Non-limiting examples of suitable water-soluble inorganic detergent builders include alkali metal carbonates, borates, phosphates,
bicarbonates, and silicates. Particular examples of this type are sodium and potassium tetraborate, bicarbonate, carbonate, orthophosphate, pyrophosphate, tripolyphosphate and metaphosphate. Examples of suitable organic alkaline detergency builders include:
(1) Water-soluble aminocarboxylates and aminopolyacetates, such as nitrilotriacetate,
glycinate, ethylenediaminetetraacetate, N-(2-hydroxyethyl)nitrilodiacetate and diethylenetriaminepentaacetate, (2) water-soluble salts of phytic acid, such as sodium and potassium phytate, (3) water-soluble polyphosphonates, e.g. sodium salt of ethane-1-hydroxy-1,1-diphosphonic acid,
Potassium and lithium salts; such as sodium, potassium and lithium salts of ethylene diphosphonic acid; (4) water-soluble polycarboxylates such as lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid; , 2-oxa-1,1,3-propanetricarboxylic acid, 1,
Salts of 1,2,2-ethanetetracarboxylic acid, mellitic acid and pyromellitic acid, and (5) U.S. Pat.
It is a water-soluble polyacetal disclosed in specification No. 4144266 and specification No. 4246495. Another type of detergency builder material useful in the present compositions is a water-soluble material that can produce water hardness cations and water-insoluble reaction products, preferably in combination with crystal seeds that can provide growth points for the reaction products. Consists of matter. A "seed builder" composition of this type is detailed in GB 1424406. Yet another class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent No. 814,874. This patent uses _the general formula Na _z (AIO ₂ ) _z ( _{SiO 2} ) y
1 and X is an integer from about 15 to about 264), the aluminosilicate having a calcium ion exchange capacity of at least 200 mg equivalents/g and at least about 2 grains/gal/min. A detergent composition having a calcium ion exchange rate of /g) is disclosed and claimed. The preferred substance is _Na12
Zeolite A is (SiO ₂ AlO ₂ ) ₁₂ 27H ₂ O. The amount of detergency builder in the bleaching composition ranges from 0% to approx.
70%, preferably about 10% to about 60%, most preferably about 20% to about 60%. Buffers can be utilized to maintain the desired alkaline PH of the bleach solution. Buffers include, but are not limited to, many of the detergency builder compounds described above. Buffers suitable for use in the present invention are well known in the cleaning art. Preferred optionally incorporated ingredients are, for example, foam modifiers, especially of the foam-inhibiting type, such as silicones and silica-silicone mixtures. US Patent Nos. 3,933,672 and 4,136,045 disclose silicone antifoam agents. Silicone materials include alkylated polysiloxane materials,
For example, silica aerogels and xerogels and various hydrophobic silicas can be used. silicone material formula where x is from about 20 to about 2000 and R and R ¹ are each an alkyl or aryl group, especially methyl, ethyl, propyl, butyl and phenyl. Approximately 200 to approx.
All polydimethylsiloxanes (R and R ¹ are methyl) having molecular weights in the range of 2,000,000 and above are useful as antifoam agents. Additional suitable silicone materials in which the side groups R and R ¹ are alkyl, aryl, or mixed alkyl or arylhydrocarbyl groups exhibit useful foam control properties. Examples of similar components are diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenyl-methylpolysiloxane, and the like. Additional useful silicone foam control agents can be mixtures of the alkylated siloxanes and solid silica. Mixtures of this type are prepared by adhering silicone to the surface of solid silica. Preferred silicone antifoam agents include hydrophobic silanized (most preferably trimethylsilanated) silica having a particle size in the range of about 10 millimicrons to 20 millimicrons and a specific surface area of about 50 m ² /g or more; Approximately 200000
With a dimethyl silicone fluid having a molecular weight in the range of approximately
It is intimately mixed at a ratio of 19:1 to about 1:2. The silicone suds suppressor is advantageously releasably incorporated into a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier. Particularly useful foam inhibitors are the self-emulsifying silicone foam inhibitors described in US Pat. No. 4,073,118. An example of this type of compound is DB-544 (siloxane/glycol copolymer), commercially available from Dow Corning. the foam modifier up to about 2% by weight of the surfactant;
Preferably, it is used in an amount of about 0.1 to about 11/2% by weight. Microcrystalline waxes having melting points in the range of 35°C to 115°C and saponification numbers less than 100 are additional examples of preferred antifoam components for use in the present compositions, and are described in U.S. Pat. No. 4,056,481. It is detailed in the specification of the No. Microcrystalline waxes are substantially water-insoluble, but water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have melting points of about 65°C to 100°C, molecular weights in the range of 400 to 1000, and
Has a penetration of at least 6 as measured by ASTM-D1321 at 77° (approximately 25°C). Suitable examples of the waxes are microcrystalline petroleum waxes and oxidized microcrystalline petroleum waxes; Fischer Tropsis wax and oxidized Fischer Tropsis wax; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax. Alkyl phosphate esters are preferred additional antifoam agents for use in the present invention. These preferred phosphate esters are primarily monostearyl phosphate (which may additionally contain distearyl phosphate and tristearyl phosphate) and monooleyl phosphate (which may contain dioleyl phosphate and trioleyl phosphate). be. Other antifoam agents useful in the practice of this invention are soaps or mixtures of soaps and nonionic surfactants as disclosed in US Pat. Nos. 2,954,347 and 2,954,348. The following examples are given to illustrate the parameters and compositions of the invention. All percentages, parts and ratios are by weight unless otherwise specified. In addition, the sodium perborate used in each of the following examples is, except for the sodium perborate monohydrate specifically described in the last example, the sodium perborate described in all other examples is It is a tetrahydrate. Example The following granular detergent composition is prepared. % C _14-15 alkyl sodium sulfate 10.1 C ₁₃ linear alkylbenzene sulfonate sodium 6.7 C _9-11 alkyl polyethoxylate _2.5 T〓 1.5 C ₁₂ alkyl trimethyl ammonium chloride
3.1 Sodium tripolyphosphate 36.0 Sodium nitrilotriacetate 3.9 Sodium carbonate 17.0 Sodium sulfate 10.1 Sodium silicate (ratio 1.6) 1.8 Water 8.1 Minor components (e.g. fragrances, optical brighteners, etc.) 1.8 〓 Stripped of lower ethoxylated fractions and fatty alcohols By adding artificial body stains to simulate the conditions of household laundry subjected to daily wear, six 5" x 5" pieces (approximately 12.7 cm x 12.7 Ten sets of swatches (cm) and five sets of four terry cloth towels were preconditioned. Each set of six swatches was then stained with a different bleach stain. Next, cut the sample in half to make 20 half-split samples.
A set was manufactured. Half of the stain was on each half of the swatch. Then one from each set of terry cloth towels
A piece of terry towel cloth was stained with a mixture of body artificial soil and vacuum cleaner soil. A wash load consisting of one set of terry cloth towels and four sets of half-swatches was placed into each of the five mini-wash systems. The four sets of half-swatches placed in each mini-wash system were selected such that no half-swatch was placed in the same mini-wash system as the other original half-swatches. The wash load in the first small wash system is reduced to 1250 ppm in the wash water, which is typical for normal automatic wash methods.
was washed with an amount of the detergent composition corresponding to . A water-type cleaning system with this type of load simulates conventional automatic cleaning methods. The washing water temperature is 37℃,
and the rinse water temperature was 22°C, and both contained a water hardness of 7 grains/gal. This cleaning method was carried out in four other mini-cleaning systems, each containing the detergent composition described above and a bleaching composition consisting of one of the following bleaching systems. A Sodium perborate Sodium acetyloxybenzene sulfonate B Sodium perborate Linear Sodium hexanoyloxybenzene sulfonate C Sodium perborate Linear octanoyloxybenzene sulfonate D Sodium perborate Linear decanoyloxybenzene Sodium Sulfonate For each of these bleaching systems, the molar ratio of hydrogen peroxide to bleach activator produced by the sodium perborate is 3 and the bleach activator added to the wash water is The amount corresponded to a maximum theoretical amount of available oxygen from percarboxylic acid of 6 ppm. Each swatch was then graded against its original other half to determine relative stain removal. -4 to 4
A rating scale of -4 indicates significantly lower stain removal, 0 indicates no difference, and 4
shows fairly high stain removal. The average rating for each stain for each mini-cleaning system was calculated. All the above operations were repeated. The average of the two measurements for each of the above averages was calculated. Finally, the average of all average values for each small cleaning system was calculated. Next, calculate the average for each system from 0 to
Scaled to 100. 0 is the mini-wash system that gave the least stain removal and 100 is the mini-wash system that gave the maximum stain removal. This number is known as the Bleaching Index. The results were as follows.

Table: Bleach compositions containing Bleach Systems B, C and D provided significantly higher stain removal than bleach compositions containing Bleach System A containing bleach activators outside the scope of the present invention. . EXAMPLE The detergent composition of the example and a bleaching composition consisting of a bleach system consisting of sodium perborate and sodium acetyloxybenzene sulfonate were placed in a beaker of water. The amounts of detergent composition and bleach activator added to the beaker of water corresponded to 1250 ppm and a maximum theoretical amount of available oxygen from percarboxylic acid of 10 ppm, respectively. The molar ratio of hydrogen peroxide to sodium acetyloxybenzenesulfonate produced by sodium perborate is 1
It was hot. The water in the beaker was 37°C and contained a water hardness of 7 grains/gal. Utilizing iodometric titration, the amount of available oxygen from the percarboxylic acid was measured 5, 10, and 15 minutes after the bleaching composition was placed in the beaker. These three measurements were averaged and then the conversion of sodium acetyloxybenzenesulfonate to percarboxylic acid was calculated. The above operation was repeated many times, but by changing the acyl group of the bleach activator and adjusting the amount of sodium perborate, the hydrogen peroxide produced by sodium perborate versus bleach activator. The molar ratio of was changed. The acyl groups were as shown below. The results were as follows.

In the case of bleach compositions containing bleach activators and bleach activators that are outside the scope of the present invention, the molar ratio of hydrogen peroxide to bleach activator produced by sodium perborate is greater than or equal to 1. The increase produces essentially no additional percarboxylic acid. Even with a ratio of 15 of this kind, the bleaching composition containing bleach activator V produces essentially no percarboxylic acid. In the case of bleach compositions containing bleach activators, and, within the scope of this invention, increasing such molar ratios by more than 1 produces significantly more percarboxylic acid. Example The following granular detergent composition was prepared.

Table: A bleaching system consisting of sodium perborate and linear sodium octanoyloxybenzene sulfonate was prepared. The stain removal ability of bleaching compositions consisting of bleaching systems of this type and detergent compositions A or B was determined by the same method as in the examples. The molar ratio of hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzenesulfonate is 3, and most of the bleach activator added to the wash water is derived from the percarboxylic acid. Maximum theoretical amount of available oxygen
This corresponded to 4.5ppm. The results were as follows.

TABLE Bleach compositions A+bleach and B+bleach within the scope of the present invention provided significantly higher stain removal than detergent compositions A and B. Example: Four sooty T-shirts were cut in half. Four T-shirt halves (none of which were in their original halves) and a 7.5 pound dirty household laundry load were placed in a conventional automatic washing machine. These fabrics are then treated with an exemplary granular detergent composition and a bleaching system consisting of sodium perborate and linear sodium octanoyloxybenzene sulfonate in amounts comparable to concentrations utilized in conventional automatic cleaning methods. Cleaned with bleaching composition. The molar ratio of hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzenesulfonate is 1, and the amount of bleach system added to the wash water is equal to the amount of oxygen from the percarboxylic acid. This corresponded to the maximum theoretical amount of 4.5 ppm. The wash water temperature was 37°C and contained a water hardness of 5 grains/gal. Using the remaining four half-split T-shirts, the above procedure was repeated without using the bleaching system, ie, using only the detergent composition. Each T-shirt half was then graded against the other half of its origin to determine the relative cleanliness of the sooty fabric. A rating scale of -4 to 4 was utilized as described in the Examples. The average of the four ratings for each cleaning system was calculated. The entire procedure was repeated three more times and the average of the average values for each wash system was calculated. This operation is repeated a number of times to prepare the bleaching composition containing the same ingredients but in different molar ratios (hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzene sulfonate). compared to bleaching compositions with This molar ratio was varied by varying the amount of sodium perborate. The average for each cleaning system was then graded from 0 to 100. 0 was the wash system that gave the worst sooty fabric cleaning and 100 was the wash system that gave the best sooty fabric cleaning. This number is known as the bleaching index. The results were as follows.

Table: Bleaching compositions having a molar ratio of hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzene sulfonate greater than 1.5 are within the scope of the present invention. It provided significantly higher cleaning of sooty fabrics than bleaching compositions with molar ratios. EXAMPLE A bleaching composition was prepared consisting of the detergent composition of the example and a bleaching system consisting of tetracetylethyldiamine (TAED) and sodium perborate.
TAED is a bleach activator well known in the bleach composition art. The molar ratio of hydrogen peroxide to TAED produced by sodium perborate is 3
It was hot. The stain removal ability of the bleaching composition was compared to the stain removal ability of the detergent composition alone by the same method as described in the Examples. The amount of bleach activator added to the wash water corresponded to a maximum theoretical amount of 3 ppm of oxygen from the percarboxylic acid. The above procedure was repeated to compare the stain removal ability of the detergent composition with a bleaching composition consisting of the detergent composition plus a bleaching system consisting of sodium perborate and linear sodium octanoyloxybenzene sulfonate. The molar ratio of hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzenesulfonate is 3, and the amount of bleach system added to the wash water is equal to the amount of oxygen from the percarboxylic acid. This corresponded to the maximum theoretical amount of 3 ppm. The results were as follows.

Table: Sodium Zenesulfonate Bleaching compositions containing linear sodium octanoyloxybenzenesulfonate provided significantly higher stain removal than bleaching compositions containing TAED. Even better performance is possible if linear sodium heptanoyloxybenzenesulfonate is used instead of linear sodium octanoyloxybenzenesulfonate. EXAMPLE The following is a granular laundry detergent composition. % C ₁₃ Sodium Alkyl Benzene Sulfonate 7.5 C _14-15 Sodium Alkyl Sulfate 7.5 C _12-13 Alkyl Polyethoxylate Stripped with Non-Ethoxylated Alcohols and Lower Ethoxylates (6.5) 2.0 C ₁₂ Alkyl Trimethylammonium Chloride
1.0 Sodium tripolyphosphate 32 Sodium carbonate 10 Sodium perborate monohydrate 5.3 Sodium octanoyloxybenzenesulfonate 5.8 Sodium diethylenetriaminepentaacetate
0.5 Sodium sulfate, H ₂ O and minor components Remainder In place of sodium diethylenetriaminepentaacetate in the formulation, the following substances are used: sodium or potassium ethylenediaminetetraacetate, N,N-di-(2-hydroxyethyl)glycine, Since the interference of heavy metal ions to the bleaching action is substantially reduced when using ethylenediaminetetra (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate), diethylenetriamine penta (methylene phosphonate) and 1:1 mixtures thereof. Virtually equivalent results are obtained.

Claims (1)

[Scope of Claims] 1 (a) An aqueous solution of hydrogen peroxide selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate peroxide, and mixtures thereof. peroxygen bleaching compounds that can be formed in and (b) the general formula (wherein R is an alkyl group having about 5 to about 18 carbon atoms, and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms, and M is a cation that confers solubility to the bleach activator), and the molar ratio of hydrogen peroxide produced by (a) to bleach activator (b) is approximately A bleaching composition characterized in that it is greater than 1.5. 2. The composition of claim 1, wherein the molar ratio of hydrogen peroxide produced by bleach activator (b) is at least about 2.0. 3. The composition of claim 1, wherein the peroxygen bleaching compound is sodium perborate monohydrate. 4. Claims in which R is an alkyl group having about 5 to about 12 carbon atoms, and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms. Composition according to item 2. 5. The composition of claim 4, wherein 5R is a linear alkyl chain having about 5 to about 9 carbon atoms. 6. The composition of claim 5, wherein 6R is a linear alkyl chain having about 6 to about 8 carbon atoms. 7 by weight, (a) producing hydrogen peroxide in aqueous solution selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbon peroxide, and mixtures thereof; Peroxygen bleaching compound capable of about 1% to about 60%, (b) General formula (wherein R is an alkyl group having about 5 to about 18 carbon atoms, and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms, and M is a cation that imparts solubility to the bleach activator) from about 0.5% to about 40% of the bleach activator (hydrogen peroxide produced by (a) vs. bleach activator (b))
(c) from about 1% to about 30% of a detergent surfactant. 8. The composition of claim 7 further comprising about 10% to about 60% detergency builder.