JPS5922999A - Bleaching composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to bleaching compositions. More particularly, 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 a whitening mechanism occurs on the fabric surface thereby removing stains and/or soils.

The bleaching compositions of the present invention contain a peroxygen bleach that can be produced in an aqueous solution of hydrogen peroxide and a specific whitening agent activator in a given molar ratio of hydrogen peroxide to bleaching agent activator. In a highly preferred embodiment, the button coating I composition of the present invention is a detergent composition.

Peracid cumulative whiteners have long been known to be effective in removing stains and stains from fabrics, but they have also long been known to be extremely temperature dependent. .

Bleaching agents of this type are essentially practical and/or effective only in bleach solutions, ie, mixtures of bleach and water, whose temperature is above about .omega..degree. At bleach temperatures of approximately 100°F, 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. I have to throw it. This is economically unfeasible. When the bleach temperature drops below 60°C, peroxygen bleach becomes ineffective regardless of whether it is added to the system.

The temperature dependence of peroxygen bleaching agent is that this type of bleaching agent (a)
It is important because it is commonly used as a detergent adjunct in fabric washing methods that utilize automatic home washing machines with wash water temperatures below 0.9°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 materials commonly referred to as bleach activators that make peroxygen bleaches effective at wax temperatures below 60°C. A number of materials have been disclosed in the art as effective bleach activators.

Background technology Carzenate ester bleach activators are known.

British Patent No. 864,798 discloses an inorganic persalt and an organic ester of an aliphatic calcinic acid (the calcinic acid ester particle size is at least 70% retained on a 60 mesh British standard sieve). sized) is disclosed. Ester with carbon number of 10 or less,
Preferably it is derived from aliphatic carbenoic acids having preferably less than 8. The ratio of molecules of reactive ester to each atom of available oxygen in the persalt is 1/4 to 4. Preferably 1/
It is 2 to 1.5. Bleaching compositions of this type are described as being stable on storage.

British Patent No. 836,988 discloses bleaching compositions containing hydrogen peroxide or an inorganic persalt and an organic carboxylic acid ester. Trials defining the esters of the invention are described. The number of ester molecules per available oxygen atom is 1/4 to 2. The patent rate is 1/2 to 1.5.

Esters of this type are described as giving improved bleaching at temperatures between 50°C and ω°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 bleaching agents, provide particularly effective surface bleaching. U.S. Pat. No. 4,283,301 discloses a peroxygen bleach and a compound of the general formula: and each 2 has a leaving (le
aving) group] is disclosed. Preferably, such bleach and bleach activator are present in equimolar ratios.

SUMMARY OF THE INVENTION The present invention provides (a) a filtered oxygen bleaching compound capable of producing hydrogen peroxide in aqueous solution, and (b) a compound having the general formula: , and the longest linear alkyl chain extending from and encompassing the carbonyl carbon has a mole number of about 6 to about 10, and L is a leaving group, and the conjugate acid is about 6
a bleach activator having a pKa in the range of about 13 to about 13, wherein the molar ratio of hydrogen peroxide produced by al to bleach activator (b) is greater than about 1.5. A bleaching composition characterized by:

The present invention relates to bleaching 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. Compositions of this type provide highly effective and efficient surface whitening of fabrics, thereby eliminating stains and/or
Dirt is removed from fabrics. The composition is particularly effective in removing sooty stains from fabrics. Sooty stains are stains that accumulate 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 that is at least about 5°C warm. Without a bleach activator, this type of peroxygen bleaching agent would be ineffective and/or inoperable at temperatures below about (a)°C.

The bleaching compositions of the present invention are extremely efficient. Achieves 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 argyl chain extending from the carzenyl carbon and including the carbonyl carbon. Therefore, on a 1 molar basis, the present invention requires only relatively small amounts 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, bleach activators are generally believed to generate percarzenic acid in response to nucleophilic overgrowth of 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 red-white component. - Heavy ring r1! It is theorized that the buildup must be generated at or near the surface of the fabric to provide surface bleaching. Otherwise - although the heavy ring oxygen would give bleaching.

Not on cloth surfaces. This type of whitening is known as solution bleaching, ie bleaching the stain in a bleach solution.

In order to ensure that singlet oxygen is efficiently generated on the fabric surface, the longest linear alkyl chain extending from the carunyl percarboxylic acid carbon and including the carunyl carbon must be It is essential to have about 6 to about 10. This type of percarboxylic acid is surface active and tends to concentrate on the surface of the particles. Percardic acids of this type, which have fewer carbons in the alkyl chain, have similar redox potency, but do not have the ability to concentrate on fabric surfaces. Therefore, the bleach activators of the present invention can achieve the same level of surface bleaching performance as similar bleach activators outside the scope of the present invention having fewer carbon numbers in the alkyl chain of this type. It is extremely efficient since, on a molar basis, only relatively small amounts of bleach activator are required.

Based on the same theory described above, the bleach activators of the present invention are capable of inhibiting peroxygen bleach even at bleach solution temperatures at which the bleach activator does not need to activate the bleach, i.e., above about ω°C. It is also conceivable that it can be made even more efficient.

Therefore, in the case of the bleach composition of the present invention, less peracid cumulative bleach is required to obtain the same level of surface bleaching performance as is obtained with peroxygen bleach alone.

The molar ratio of hydrogen peroxide to bleach activator produced by the 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. Approximately 1.
For molar ratios of such components below 5, there are predominantly competitive chemical reactions that take place.

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. 1 Surface bleaching performance is therefore enhanced especially for sooty fabrics.

Power/I/y)? The longest linear alkyl chain extending from the nyl carbon and encompassing the carzenyl carbon is shorter (i.e., C2
~5) or longer (i.e., C1 or longer), and thus are similar to the fabric bleach activators of the present invention but outside the scope of the present invention. No significant amount of percarboxylic acid is produced when increasing the molar ratio of hydrogen oxide to bleach activator above 1.5. For bleach activators of this type with short (-alkyl chains), practical evidence suggests that the molar ratio of hydrogen peroxide produced by peroxygen bleach to bleach activator of 1 is essential. Theoretically, the theoretical maximum percarboxylic acid produced means that the percarboxylic acid produced will not react with the unreacted bleach activator.Therefore, the addition of more peracid bleach would not provide additional percarboxylic acid.The experimental evidence in the case of this plum bleach activator with a more alkyl chain is that even if very much peroxygen bleach is added. This shows that only useless percarboxylic acids are produced in the end regardless of the name of the peroxygen bleach activator. It is believed that the percalzic acid warps with the unreacted bleach activator to form diacylperoxy 7P.Only the bleach activator of the present invention has a ca.
be advantageously influenced by the molar ratio of hydrogen peroxide to bleach activator produced by peroxygen bleaching greater than 5.

There is essentially no upper limit to this type of molar ratio, since adding more peracid shavings is not harmful 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 whitening agent is economically impractical or undesirable. However, it is not necessary for the bleach activator to activate the peroxygen bleach at a bleaching solution temperature of 60°C.
When brewing at higher levels, more peroxygen whitening agent can be added and provides additional benefits. This is especially true under European cleaning conditions that utilize "boiling water." 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 concentrates 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 to 10. Not only to optimize surface bleaching performance, but also to prevent the bleaching solution from having an undesirable odor.
p) (is preferably higher than 9. It has been observed that when the pH of the bleach solution falls below 9, the bleach solution begins to have an undesirable odor. It is obtained using substances commonly known as buffers, which are optional components of the composition.

The following is a specific description of the essential and optional ingredients of the bleaching composition of the present invention. all 5
Peroxygen bleaching compounds useful in the present invention are those 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 peroxide base, and inorganic peroxide resistant bleaching compounds such as alkali metal peroxides. Acid salts include percarbonate, superphosphate, etc.

If desired, warm mixtures of two or more such clarifying compounds can also be used.

Preferred peroxygen bleaching compounds are, for example, sodium perborate, sodium carbonate, and hydrogen peroxide, which are commercially available in the hydrate and tetrahydrate forms.

These are sodium birophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide. Particular preference is given to sodium perborate tetrahydrate and especially sodium perborate hydrate. Sodium perborate hydrate 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 percarzenic acid and therefore enhances surface bleaching performance.

The amount of peracid cumulative bleach within the compositions of the present invention ranges from about 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 1%.

Bleach Activators The bleach activators of the present invention have the general formula (wherein R is an alkyl group having from about 5 to about 18 carbon atoms, and the longest linear alkyl group extending from the carzenyl carbon and encompassing the carzenyl carbon). The chain has a carbon number of about 6 to about IO, and L is a leaving group, and the conjugate acid has a pKa in the range of about 6 to about 13.

L can be essentially any suitable leaving group. A leaving group is a group that is displaced from the bleach activator (d 15place ) as a result of nucleophilic attack on the bleach activator by a perhydroxide ion. This, or perhydrolysis, produces percarzenic acid. in general,
For a group to be a suitable ping group, it must produce an electron-withdrawing effect. This facilitates nucleophilic attack by the perhydroxide anion. Leaving groups exhibiting this type of behavior are those whose conjugate acid ranges from about 6 to about 13, preferably from about 7 to about 11. Most preferably those have a pKa of about 8 to about 11.

Preferred bleach activators are where R is as described in the general formula above and L is y.

(wherein R is as defined above, R2 is an alkyl chain having from about 1 to about 8 carbon atoms, R3 is H or R, and Y is H or a solubilizing group) selected from the group. A preferred solubilizing group is -8
o3-M", -Coo-M+, -8o4-M+, (-N
4-R3')X- and 04-NR2', most preferably -803-M+ and -COO-M+ (
R' is an alkyl chain having about 1 to about 4 carbon atoms;
is the cation that confers solubility to the bleach activator, and X is the anion that confers solubility to the bleach activator)
. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion. It should be noted that bleach activators with leaving groups that do not contain solubilizing groups should be well dispersed within the bleach solution to facilitate their dissolution.

Also, preferred bleach activators are such that L is as described in the general formula above, and R is an alkyl group having from about 5 to about 12 carbon atoms, and the longest line extending from and including the carbonyl carbon is The alkyl chain has about 6 or more carbon atoms.
of the general formula having about 10.

L is as described in the general formula above, and R has about 5 to about 9 carbon atoms. More preferred are whitening agent activators of the above general formula, preferably having from about 6 to about 8 linear alkyl chains.

More preferred bleach activators include R having about 5 to about 9 carbon atoms.
preferably a linear alkyl chain having from about 6 to about 8;
And L is Y
O (wherein R, R, R and Y are as defined above) is of the above general formula selected from the group consisting of:

Particularly preferred Zhaobai agent activators are those in which R is an alkyl group having 5 to 12 carbon atoms, and the longest linear portion of the alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms; [In the formula, R2 is as described above, and Y is -M+ or -Coo
-M-'' (M is as described above)] is a Moeki general formula selected from the group consisting of.

Particularly preferred bleach activators have R of from about 5 to about 9 carbon atoms.
preferably a linear alkyl chain having from about 6 to about 8;
and L is [wherein R is as described above, and Y is -8o3M
or -COOMCM is as described above)] of the above general formula.

The most preferred stimulant activators have formula 1 (wherein R is about 5 to about 9 carbon atoms, preferably about 6 to about 8 carbon atoms).
and M is sodium or potassium).

The amount of whitener activator within the compositions of the present invention ranges from about 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 5% to about 20%.

Optionally Incorporated Components As a preferred embodiment, the whitening 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, crystal white compositions are particularly effective. The bleaching compositions of the present invention can contain all the usual ingredients of detergent compositions, such as those described in U.S. Pat. No. 3,936,537.

The components of this sleep are, for example, colored speckles (colo).
r 5peckles), foam enhancer, foam inhibitor, g
Corrosion inhibitors and/or corrosion inhibitors, soil suspending agents.

Stain release agents, dyes, fillers, optical brighteners, bactericides.

These include alkalinity sources, hyprotropes, antioxidants, enzymes, fermentation stabilizers, and fragrances.

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 are:

No. 3,664,961 and US Pat. No. 3,919,678. Useful cationic surfactants include, for example, U.S. Pat.
,905 and U.S. Pat. No. 4,239,659.
It is described in Book No. IvIII. 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. This is an alkali metal soap with a carbon number of about 8 to about 24. Preferably about 1 carbon number
These are sodium salts, potassium salts, ammonium salts, and alkylol ammonium salts of higher fatty acids having a molecular weight of 2 to about 18. Soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are mixtures of fatty acids derived from coconut oil and tallow. IJum salts and potassium salts, ie, sodium or potassium tallow soaps and coconut soaps.

Also useful anionic surfactants include, for example, water-bathable salts of permeable sulfuric acid reaction products having alkyl groups of from about 12 to about 100 carbon atoms and sulfonate or sulfate ester groups in their molecular structure. , preferably an alkali metal salt,
In ammonium salts and alkylol ammonium salts, aro(r-alkyl) includes the alkyl moiety of the ryonru group. Examples of synthetic surfactants in this group are higher alcohols (C8-C18 carbon ?
M[obtained by oxidizing the
Sodium alkylbenzene sulfonates and potassium alkylbenzene sulfonates having 5, e.g., U.S. Pat.
It is of the type described in No. 383 Specification 1. Linear linear argylbenzene sulfonate whose average number of carbon atoms in the alkyl group is approximately 11 N13 (abbreviation C1□~13LAS)
is especially valuable.

Other anionic surfactants are sodium argyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglycerides sulfonate and sodium coconut oil fatty acid monoglyceride sulfonate: Sodium or potassium salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxy 7P per molecule and having an alkyl group of from about 8 to about 12 carbon atoms; and from about 1 to about 1 per molecule It is a sodium salt or potassium salt of trigyl ethylene oxide 7-doether sulfate containing about 10 units of ethyleneoxy P and having an alkyl group having about 12 to about 10 carbon atoms.

Other anionic surfactants useful in the present invention include, for example, esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester chain. Water-soluble salt of 2-ryosiloki/alkane-1-sulfonic acid having 2 to 9 carbon atoms in the afur makuuchi and about 9 to about 23 carbon atoms in the alkaf part; 12 to 20 carbon atoms water-soluble salts of olefin sulfonic acid and nozorafuinsulfonic acid having 1 to 3 carbon atoms in the alkyl group and 8 carbon atoms in the alkaf moiety;
N20 is W-j'le β-argyloquialkanesulfonate.

Water-inhibiting 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 i-halalkyleneoxy P 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 tailored 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.

e.g. 6 carbon atoms either before the straight or branched arrangement
It is a condensation product of an alkylphenol having an alkyl group having -15 and about 3 to 12 moles of ethylene oxide per mole and a half of argylphenol.

Preferably, the non-ionic surfactant is a water-dissolvable and water-dispersible condensation of an aliphatic alcohol having 8 to 22 carbon atoms in either a chain or branched configuration with 3 to 12 moles of ethylene oxide per mole of alcohol. It is a thing. Particularly preferred are compounds of alcohols containing argyl groups having 9 to 15 carbon atoms and about 4 to 8 moles of ethylene oxide per mole of alcohol.

A semi-sandy nonionic surfactant, for example, has a carbon number of 10 to 1.
1 alkyl moiety of 8 and about 1 to about 3 carbon atoms
a water-bathable amine oxide containing two moieties selected from the group consisting of a moiety of about 10 to 18 carbon atoms and a hydroxyalkyl moiety of about 10 to 18 carbon atoms;
a water-bathable phosphineoxy P containing two moieties selected from the group consisting of an alkyl group having an alkyl group of 3 and a hydroxyl group; and one alkyl moiety having a carbon number of 10\18 and a carbon number of 1\3 and a hydroquinoalkyl moiety.

Amphoteric surfactants can be used, for example, in which the aliphatic moiety can be linear or branched and one of the aliphatic substituents has 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 bathing groups.

Zwitterionic surfactants are, for example, aliphatic quaternary ammonium compounds in which one of the aliphatic substituents has a carbon number of 8 to 18;
They are derivatives of phosphonium compounds and sulfonium compounds.

The amount of detergent surfactant that can be used is from 0.00 to about 50%, preferably from about 1 to about 5% by weight, and most preferably from about 10 to about 5% by weight of the total composition.

In addition to detergent surfactants, detergency builders can be used in bleaching compositions. Water bath 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 detergents include alkali metal carbonates, borates,
phosphates, bicarbonates, and silicates. Specific examples of this kind are sodium and potassium tetraborate,
carbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.

Examples of suitable organic alkaline detergent capilders are (1) water-soluble aminocalcequilates and aminopolyacetates, such as nitrilotriacetate.

Glycinate, ethylene diamine triacetate, N
-(2-Hydroxyethyl)nitrilodiacetate and diethylenetriaminepentaacetate, +21 Water-bathable salts of phytic acid, such as phytin +'R sodium and potassium phytate, (3) Water-soluble? Liphosphonates 1, such as sodium, potassium and lithium salts of ethane-1-hydroquine-1,1-diphosphonic acid; sodium, potassium and lithium salts of ethylenediphosphonic acid, etc. (4) Water-soluble molasses Xylates such as lactic acid, succinic acid, malonic acid, maleic acid, citric acid.

Calzegicimethyloxysuccinic acid, 2-oxa-1,1
, 3-gallon tricarzenic acid, 1. i, salts of 2°2-ethanetetracarzenic acid, mellitic acid and pyromellitic acid, and (5) water bathing properties as disclosed in U.S. Pat. Nos. 4,144,266 and 4,246,495. It is polyacetal.

Another type of detergency builder material useful in the present compositions is capable of producing 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 m-type substances. A "seed builder" composition of this type is detailed in British Patent No. 1.424,406.

Yet another type of detergency builder material useful in the present invention is:
Insoluble sodium aluminosilicate, especially Herky Patent No. 814,874! 1IJ1%tvc. This patent describes the general formula % (where 2 and y are integers equal to at least 6, the molar ratio of 2 to y is within the range of 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264) (said aluminosilicate has a concentration of at least 200 mg/l of cal/lam ion father conversion blue and at least about 2 g/gal/min/
A detergent composition having a cal/lam ion father exchange rate of I) is disclosed and is desired. A preferred material is zeolite A, which is Na1□(SiO□A10□)1□27H20.

The amount of detergency builder in the bleaching composition is from 0% to about 70%;
Preferably it is about 200% to about (a)%, most preferably about 1% to about 60%.

To maintain the desired alkaline pH of the bleach solution.

Buffers are available. 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 those of the foam-inhibiting type, such as 7-licone and Noricur 7-licone combinations.

U.S. Pat. No. 3,933,672 and 4.1
No. 36,045 discloses 7 silicone antifoam agents. The silicone materials can be algylated boronoxane materials such as aerogels and xerogels and various hydrophobic silicas. The silicone material has the formula: where X is from about 0 to about 2,000, and R and R are each an alkyl or aryl group, particularly methyl,
ethyl, propyl, butyl and phenyl). Approximately 200 to approximately 2.0
Polydimethylsiloxane (R and R1 are methyl) having a molecular weight within and above 00,000
are all useful as antifoam agents. Certain additional suitable silicone materials with side chain groups R and R or alkyl, aryl, or mixed argyl or arylcarbyl groups exhibit useful foam control properties. Examples of similar components are diethyl-
, dipropyl-, diptyl-, methyl-, ethyl-, phenyl-methylpolysiloxane and the like. Additional useful silicone foam control agents can be mixtures of the alkylated siloxanes and solid foams.

Mixtures of this type are prepared by adhering silicone to the surface of a solid material. Preferred SiIJ cone antifoam agents have particle sizes in the range of about 10 millimicrons to about 10 millimicrons and about 50 m2/! A hydrophobic 7-ran (most preferably trimethyl 7-ran) adhesive having a specific surface area greater than or equal to i and a dimethyl silicone fluid having a molecular weight within the range of about 500 to about 200,000 are combined with silicone vs. 7-ran silica. They were intimately mixed in a weight ratio of 19=1 to about 1:2. The silicone suds suppressor is advantageously incorporated into the water-bathable or water-dispersible, substantially non-surface-active, detergent-impermeable gear in a separable manner.

A particularly useful foam inhibitor is the self-emulsifying 7 silicone foam inhibitor described in U.S. Pat. No. 4,073,118.

An example of this type of compound is B-544 (siloxane/glycol copolymer), commercially available from Dow Corning.

The foam modifier is added up to about 2% by weight of the surfactant, preferably from about 1 to about 1-! -Used in weight percent.

A microcrystalline wax having a melting point in the range of 35°C to 115°C and a saponification number of less than 100 is
Additional examples of preferred antifoam components for use in the present compositions and disclosed in U.S. Pat. No. 4,056,481? R.B.
detailed in the book. Although microcrystalline waxes are substantially water-inacidic.

Water dispersible in the presence of organic surfactants.

Preferred microcrystalline waxes are from about 65°C to 1
Melting point of 00℃, molecular weight within the range of 400-1000.

and 77°F (approximately 3°C) per ASTM-D 1321.
) has at least 60 stitches. Suitable examples of said waxes are microcrystalline petroleum wax and oxidized microcrystalline petroleum wax; Fischertrop 7 wax and oxidized Fischertropsch wax; osikerite; Cele 7/; 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 principally monostearyl phosphate (which may additionally contain distearyl phosphate and hydryl ester phosphate) and monooleyl phosphate (which may contain dioleyl phosphate and trioleyl phosphate).

Other antifoam agents useful in the practice of this invention include U.S. Pat.
54,347 and 2,954,348, or a mixture of soap and a nonionic surfactant.

The following examples are given to illustrate the chlorine meters and compositions of the present invention. All parts and proportions are by weight unless otherwise specified.

Example I The following granular detergent composition is prepared.

C14-1. Sodium alkyl sulfate 10
．． 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* By adding artificial body stains to simulate the conditions of household laundry subjected to daily wear, stripped of lower ethoxylated fractions and fatty alcohols, six standard fabrics were prepared. 5 inches x 5 inches (approx. 12.7 cm)
x approximately 12.7 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, the sample was cut in half to create a half-split Kojimoto Kagumi. Half of the stain was on each half of the swatch. One terry towel cloth from each set of terry cloth towels was then stained with a mixture of body artificial soil and vacuum cleaner soil.

A wash load <1 oad) 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.

A laundry load in a first compact wash system was washed with an amount of the detergent composition equivalent to 12501) pm in the wash water, which is typical in conventional automatic washing methods. A small wash 7 stem with this type of load simulates a normal automatic wash method. The wash water temperature is 37℃, and the rinse water temperature is 2.
2° C. and both contained a water hardness of 7 grains/gal.

This cleaning method was carried out in four other mini-wash 7 stems, each mini-wash system containing the detergent composition and a bleaching composition consisting of one of the following bleaching systems:
Ta.

Sodium Perborate Acetyloxy/Sodium Benzene Sulfonate Sodium Perborate Linear Sodium Perborate Linear Octanoyloxybenzenesulfonate Sodium Perborate Linear Decanoyl Sodium Perborate Sodium Oxybenzenesulfonate 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. The amount of is the maximum theoretical amount of available oxygen from percaric acid 6pp
It corresponded to m.

Next, each sample was graded relative to the other half of its original to determine relative stain removal. A rating scale of -4 to 4 is used, with -4 indicating fairly low stain removal, 0 indicating no difference, and 4 indicating fairly high stain removal. The average grade of each stain case for each small 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 wash 7 stem case was calculated. It was then scaled to an average of 0 to 100 for each system. O
is the mini-wash/stem that gave the least stain removal and 100 is the mini-wash system that gave the maximum stain removal. This number is the bleaching index (Bleacbing 1n
dex).

The results were as follows.

AB CD No Bleach Bleach Index 19 52 100 91 0 Bleaching compositions containing bleaching systems B, C and D are superior to bleaching compositions containing bleaching system A containing bleach activators outside the scope of the present invention. Also gave significantly higher stain removal.

EXAMPLE ■ A bleach composition consisting of the detergent composition of Example I and a bleach system consisting of sodium perborate and sodium acetyloxy/benzenesulfonate was placed in a beaker of water. The detergent composition and bleach activator added to the beaker of water corresponded to a theoretical maximum of 1250 ppm and 10 ppm of available oxygen from percarzenic acid, respectively. The molar ratio of sodium cetyloxybenzenesulfonate to hydrogen peroxide produced by sodium perborate was 1. The water in the beaker was 37° C. and contained a water hardness of 7 grains/gal.

Using an iodometric titration method, the amount of available oxygen from calzenic acid was measured at 10 minutes after the bleaching composition was added to the beaker.
Measurements were taken after minutes and 15 minutes. These three measured values were averaged and the conversion rate of sodium acetyloxy-7benzenesulfonate to percarzeneic acid was subtracted by one order.

The above procedure was repeated many times, but by changing the acyl group of the bleach activator and adjusting the amount of sodium perborate, the difference between hydrogen peroxide produced by sodium perborate and bleach activator was reduced. The molar ratio was changed. The acyl group was as shown below.

The results were as follows.

1:1 2:l 3:1 4:] 15:1 bleach activator ■ Acetyl 95 --- 95 ---
---■Linear hexanoyl 85 --- 92 ---
- -1-■ Linear heptanoyl 60 70 98
--- ---■ Linear octanoyl 50 70 8
3 90 ---~ Decanoyl 40 ---
- 58 --- ---Vl Dodecanoyl
2 --- 4 --- 0 Hydrogen peroxide versus bleach activator produced by sodium perborate in the case of silver-white compositions containing bleach activators I and V, which are outside the scope of the present invention Increasing the molar ratio by more than 1 essentially does not generate any additional percarboxylic acid. Even with a ratio of 15 of this kind, a whitening composition containing a whitening agent activator produces essentially no percarboxylic acid. In the case of whitening compositions containing bleach activators I, I and IV within the scope of this invention, increasing the molar ratio of these species by more than 1 produces significantly more percarboxylic acids.

Example +11 Pl the following granular detergent composition! ! ! Made by I.

B C16-18 alkyl sodium sulfate 5.5%
O%CI4～Yo, Sodium Argyl Sulfate 0
10.7 Tori, tf Sodium Liphosphate
24.4 38.0 Sodium nitrilotriacetate
0 4.1 Zeolite A
I7.6 0 Sodium carbonate
10,5 12.0 Sodium silicate (ratio 2.0
) 1.9 0 Sodium silicate (ratio 1
．． 6) 0 1.9 Sodium sulfate
21.0 10.7 Wednesday
8.9 8.5 Minor Ingredients 1.2 1.8 A bleaching system consisting of sodium perborate and linear sodium octanoyl oxbenzene sulfonate was prepared.

The stain removal ability of the bleaching compositions of this type of bleaching system and detergent compositions A or B was determined by the same method as in Example I. The molar ratio of water peroxide produced by sodium perborate to linear sodium octanoyloxybenzene sulfonate is 3, and the amount of bleach activator added to the wash water is equal to the effective amount from the percarboxylic acid. This corresponded to a maximum theoretical amount of oxygen of 4.5 ppm.

The results were as follows.

Whitening finger ridge 0 10 10 (J 9
1. Bleach composition A within the scope of the present invention Bleach agent and B
Ten Bleach provided significantly higher stain removal than detergent compositions A and B.

Example ■ Four sooty T-shirts were cut in half. Four t-shirts (none of which were in their original halves) and 7.5 lbs. of dirty home t-shirts were removed from a normal auto. I put it in the washing machine. These fabrics were then treated with a bleaching system consisting of the granular detergent composition of Example 1 and sodium perborate and linear sodium octanoyl ox-7benzenesulfonate in an amount corresponding to the concentration utilized in conventional automatic cleaning methods. It was washed with the bleaching Mi composition contained therein.

The molar ratio of hydrogen peroxide to linear sodium octanoyloxybenzene sulfonate produced by sodium perborate is 1, and the bleach system needle added to the wash water has a maximum theoretical yield of oxygen from the percarboxylic acid. Amount 4.5ppm
It was equivalent to The wash water temperature was 37°C and contained a water hardness of 5 grains/gal.

The procedure was repeated using the remaining four T-shirt halves and using no bleaching system, ie, using only the detergent composition.

Each T7 half was then graded relative to its original other half to determine the relative cleanliness of the sooty fabric.

A -4 to 4 rating scale was utilized as described in Example IK. The average of the four ratings for each cleaning system was calculated.

All of the above operations were repeated three more times, and the average of the above average values for each cleaning system was calculated by 1F.

This operation is repeated a number of times to prepare the bleaching composition containing the same components but with different molar ratios (hydrogen peroxide produced by sodium perborate to linear sodium octanoyloxybenzene sulfonate). compared to bleaching compositions. This molar ratio was varied by varying the amount of sodium perborate. The average value for each cleaning system was then graded from 0 to 100. 0 is the cleaning system that gave the lowest sooty fabric cleaning, and 1
00 &'! It was a cleaning system that gave the best sooty fabric cleaning. This number is known as the bleaching index.

The results were as follows.

Detergent composition only 0 201・0
38 201.5
29 202.0
65 203.0 100
204.0 82 20
Bleaching compositions having a molar ratio of hydrogen peroxide produced by sodium perborate to linear octanoyloxy/sodium benzenesulfonate greater than 1.5 are within the scope of this invention. It provided significantly higher cleaning of sooty fabrics than bleaching compositions with molar ratios.

Example X The detergent composition of Example I and tetracetylethyldiamine (
A bleaching composition was prepared consisting of a bleaching system consisting of 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 was 3.

The stain removal ability of the detergent composition was compared to the stain removal ability of the detergent composition alone by the same method as described in Example I. The amount of whitening agent activator added to the wash water corresponded to a maximum theoretical amount of oxygen from percarboxylic acid of 3 ppm.

The above procedure was repeated to compare the stain removal ability of the detergent composition with a moth whitening composition comprising a bleaching system comprising sodium decaperborate and sodium linear octanoyloxybenzene sulfonate. The molar ratio of hydrogen peroxide to linear sodium octanoyl oxbenzene sulfonate produced by sodium borate is 3;
The amount of bleach system added to the wash water then corresponded to a theoretical maximum of 13 ppm of oxygen from percarzene acid.

The results were as follows.

No bleach 0 33TAED
33 33 Bleaching compositions containing linear sodium octanoyloxybenzene sulfonate provided significantly higher stain removal than bleaching compositions containing TAED. When using linear sodium hezotanoyloxybenzenesulfonate instead of linear sodium octanoyloxybenzenesulfonate,
Even better performance is possible.

Example Vl The following is a granular laundry cleaning silicon composition.

% Sodium C13 alkylbenzenesulfonate 7
．． 5CI4-15alkyl sodium sulfate
7.5C1□Alkyltrimethylammonium chloride P 1.0 tri? Sodium lyphosphate
32 Sodium carbonate 10
Sodium perborate hydrate 5.3 Octanoyloxybenzenesulfone 5. Sodium octate diethylenetriamine pentaacetate 0.
5 sulfuric acid) IJum% HO and small amounts of components Remaining
In place of diethylenetriaminepentaacetate in the above formulations, the following substances are added: sodium or potassium ethylenediaminetetraacetate, N
, N-di(2-ethyl) glycine, ethyl nondiaminetetra (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate)
, diethylenetriamine penta(methylene phosphonate) and 1=1 mixtures thereof, substantially equivalent results are obtained since the interference of heavy metal ions with the bleaching action is substantially reduced.

Claims (1)

[Scope of Claims] 1. (a) A bleaching compound capable of producing hydrogen peroxide in an aqueous solution and (b) having a general formula (wherein R is an alkyl group having about 5 to about 18 carbon atoms; ,
Moreover, the longest linear alkyl chain extending from the carzenyl carbon and wrapping around the carzenyl carbon has about 6 to about IO carbon atoms, and L is a leaping group, and its conjugate acid is about 6 to about IO. a bleach activator having a pKa in the range of about 13), and the molar ratio of hydrogen peroxide produced by (a) to bleach activator (b) is greater than about 1.5 ( 2. A bleaching composition according to claim 1, wherein the molar ratio of hydrogen peroxide to bleach activator (bl) produced by (a) is at least about 2.0. Composition. The three peracid bleaching compounds are sodium perborate hydrate,
Claim 1 selected from the group consisting of sodium perborate tetrahydrate, sodium carbonate peroxide, sodium birophosphate peroxide, urea peroxide, sodium peroxide and mixtures thereof. The composition described in. 4. The composition according to claim 4, wherein the peracid rate bleaching compound is sodium perborate hydrate. 5. L is a leaving group, and its conjugate acid ranges from about 7 to about 11. The composition according to claim 2, having a pKa of 7. The composition according to claim 2, wherein L is Y.
O (wherein R is as described in claim 1, and R is an alkyl chain having about 1 to about 8 carbon atoms)
2. A composition according to claim 1, wherein R3 is H or R2 and Y is H or a solubilizing group. 8, Y is -803''-M+, -Coo-fly, -
5o4-yr'% (-N+R')X- and 0←NR
2 and their adulterated compounds (wherein R4 is an alkyl chain having about 1 to about 4 carbon atoms, M is a cation that imparts solubility to the bleach activator, and X is a cation that imparts solubility to the bleach activator. 8. A composition according to claim 7, wherein the composition is an anion that imparts solubility to the agent. 9. A claim in which Y is selected from the group consisting of -so -y'', -coo-1oyohisohr;) mixture, where 1M is selected from the group consisting of sodium, potassium and mixtures thereof. 10. The composition according to item 8, wherein L is an alkyl chain having from about 1 to about 8 carbon atoms, and Y is -803"'M+ or -Coo-M" (M
is sodium or potassium). 11. The composition of claim 10, wherein L has the general formula: where M is sodium or potassium. 12. A patent in which R is an argyl group having 5 to about 12 carbon atoms, and the longest linear alkyl chain extending from the ruzenyl carbon and including the kartonyl carbon has about 6 to about 10 carbon atoms. A composition according to claim 2. 13. The composition of claim 12, wherein R is a linear alkyl chain having from about 5 to about 9 carbon atoms. 14. The composition of claim 13, wherein R is a linear alkyl chain having from about 6 to about 8 carbon atoms. 15, R is an alkyl group having about 5 to about 12 carbon atoms, and the longest linear alkyl chain including the nyl carbon has about 6 to about 10 carbon atoms; , and L is [wherein IL2 is an alkyl chain having about 1 to about 8 carbon atoms, and Y is 18O3''-M+ or 1000-M+
(M is sodium or potassium). 16. The composition of claim 15, wherein R is a linear alkyl chain having about 5 to about 9 carbon atoms. 17. The composition of claim 16, wherein R is a linear alkyl chain having from about 6 to about 8 carbon atoms. 18, R is an alkyl group having about 5 to about 12 carbon atoms, and the longest linear alkyl chain extending from the cycamoruzenyl carbon and including the cartonyl carbon has about 6 to about 10 carbon atoms; and L has the general formula where 1M is sodium or potassium. 19. The composition of claim 18, wherein R is a linear alkyl chain having from about 5 to about 9 carbon atoms. 20. The composition of claim 19, wherein R is a linear alkyl chain having from about 6 to about 8 carbon atoms. 21, Shigemon, (al) A peroxygen bleaching compound capable of producing hydrogen peroxide in an aqueous solution of about 1% to about 60%. (b) General formula (wherein R is an argyl group having about 5 to about 18 carbon atoms) and
Moreover, the longest linear alkyl chain contained in the carzenyl carbon has about 6 to about 10 carbon atoms, and L is a leaving group, and its conjugate acid has about 6 to about 13 carbon atoms. from about 0.5% to about 40% (the molar ratio of hydrogen peroxide to bleach activator (bl) produced by (a) is less than about 1.5). and (C) from about 1% to about 30% detergent surfactant. 22. from about 10% to about % detergent surfactant. The composition described in Section.